Impact of kerogen heterogeneity on sorption of organic pollutants. 2. Sorption equilibria

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yang, C.; Yu, Z.Q.; Xiao, B.H.

2009-08-15

Phenanthrene and naphthalene sorption isotherms were measured for three different series of kerogen materials using completely mixed batch reactors. Sorption isotherms were nonlinear for each sorbate-sorbent system, and the Freundlich isotherm equation fit the sorption data well. The Freundlich isotherm linearity parameter n ranged from 0.192 to 0.729 for phenanthrene and from 0.389 to 0.731 for naphthalene. The n values correlated linearly with rigidity and aromaticity of the kerogen matrix, but the single-point, organic carbon-normalized distribution coefficients varied dramatically among the tested sorbents. A dual-mode sorption equation consisting of a linear partitioning domain and a Langmuir adsorption domain adequately quantifiedmore » the overall sorption equilibrium for each sorbent-sorbate system. Both models fit the data well, with r{sup 2} values of 0.965 to 0.996 for the Freundlich model and 0.963 to 0.997 for the dual-mode model for the phenanthrene sorption isotherms. The dual-mode model fitting results showed that as the rigidity and aromaticity of the kerogen matrix increased, the contribution of the linear partitioning domain to the overall sorption equilibrium decreased, whereas the contribution of the Langmuir adsorption domain increased. The present study suggested that kerogen materials found in soils and sediments should not be treated as a single, unified, carbonaceous sorbent phase.« less

Micropore clogging by leachable pyrogenic organic carbon: A new perspective on sorption irreversibility and kinetics of hydrophobic organic contaminants to black carbon.

PubMed

Wang, Bingyu; Zhang, Wei; Li, Hui; Fu, Heyun; Qu, Xiaolei; Zhu, Dongqiang

2017-01-01

Black carbon (BC) plays a crucial role in sequestering hydrophobic organic contaminants in the environment. This study investigated key factors and mechanisms controlling nonideal sorption (e.g., sorption irreversibility and slow kinetics) of model hydrophobic organic contaminants (nitrobenzene, naphthalene, and atrazine) by rice-straw-derived BC. After removing the fraction of leachable pyrogenic organic carbon (LPyOC) (referring to composites of dissoluble non-condensed organic carbon and associated mineral components) with deionized water or 0.5 M NaOH, sorption of these sorbates to BC was enhanced. The sorption enhancement was positively correlated with sorbate molecular size in the order of atrazine > naphthalene > nitrobenzene. The removal of LPyOC also accelerated sorption kinetics and reduced sorption irreversibility. These observations were attributed to increased accessibility of BC micropores initially clogged by the LPyOC. Comparison of BC pore size distributions before and after atrazine sorption further suggested that the sorbate molecules preferred to access the micropores that were more open, and the micropore accessibility was enhanced by the removal of LPyOC. Consistently, the sorption of nitrobenzene and atrazine to template-synthesized mesoporous carbon (CMK3), a model sorbent with homogeneous pore structures, showed decreased kinetics, but increased irreversibility by impregnating sorbent pores with surface-grafted alkylamino groups and by subsequent loading of humic acid. These findings indicated an important and previously unrecognized role of LPyOC (i.e., micropore clogging) in the nonideal sorption of organic contaminants to BC. Copyright © 2016 Elsevier Ltd. All rights reserved.

Effects of salinity and organic matter on the partitioning of perfluoroalkyl acid (PFAs) to clay particles.

PubMed

Jeon, Junho; Kannan, Kurunthachalam; Lim, Byung J; An, Kwang Guk; Kim, Sang Don

2011-06-01

The influence of salinity and organic matter on the distribution coefficient (K(d)) for perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) in a brackish water-clay system was studied. The distribution coefficients (K(d)) for PFAs onto inorganic clay surfaces increased with salinity, providing evidence for electrostatic interaction for the sorption of PFAs, whereas the relationship between K(d) and organic carbon content (f(oc)) suggested that hydrophobic interaction is the primary driving force for the sorption of PFAs onto organic matter. The organic carbon normalized adsorption coefficient (K(oc)) of PFAs can be slightly overestimated due to the electrostatic interaction within uncoated inorganic surfaces. In addition, the dissolved organic matter released from coated clay particles seemed to solvate PFA molecules in solution, which contributed to a decrease in K(d). A positive relationship between K(d) and salinity was apparent, but an empirical relationship for the 'salting-out' effect was not evident. The K(d) values of PFAs are relatively small compared with those reported for persistent organic pollutants. Thus, sorption may not be a significant route of mass transfer of PFAs from water columns in estuarine environments. However, enhancement of sorption of PFAs to particulate matter at high salinity values could evoke potential risks to benthic organisms in estuarine areas.

Soil-adjusted sorption isotherms for arsenic(V) and vanadium(V)

NASA Astrophysics Data System (ADS)

Rückamp, Daniel; Utermann, Jens; Florian Stange, Claus

2017-04-01

The sorption characteristic of a soil is usually determined by fitting a sorption isotherm model to laboratory data. However, such sorption isotherms are only valid for the studied soil and cannot be transferred to other soils. For this reason, a soil-adjusted sorption isotherm can be calculated by using the data of several soils. Such soil-adjusted sorption isotherms exist for cationic heavy metals, but are lacking for heavy metal oxyanions. Hence, the aim of this study is to establish soil-adjusted sorption isotherms for the oxyanions arsenate (arsenic(V)) and vanadate (vanadium(V)). For the laboratory experiment, 119 soils (samples from top- and subsoils) typical for Germany were chosen. The batch experiments were conducted with six concentrations of arsenic(V) and vanadium(V), respectively. By using the laboratory data, sorption isotherms for each soil were derived. Then, the soil-adjusted sorption isotherms were calculated by non-linear regression of the sorption isotherms with additional soil parameters. The results indicated a correlation between the sorption strength and oxalate-extractable iron, organic carbon, clay, and electrical conductivity for both, arsenic and vanadium. However, organic carbon had a negative regression coefficient. As total organic carbon was correlated with dissolved organic carbon; we attribute this observation to an effect of higher amounts of dissolved organic substances. We conclude that these soil-adjusted sorption isotherms can be used to assess the potential of soils to adsorb arsenic(V) and vanadium(V) without performing time-consuming sorption experiments.

Rates and equilibria of perfluorooctanoate (PFOA) sorption on soils from different regions of China.

PubMed

Miao, Yu; Guo, Xuetao; Dan Peng; Fan, Tingyu; Yang, Chen

2017-05-01

Understanding sorption of PFOA on soil particles is crucial to evaluate its environmental risk. Here, sorption of PFOA onto ten agricultural soils was examined. The influence of soil physico-chemical properties on PFOA sorption was investigated. The sorption rate of PFOA followed a pseudo-second-order kinetics. Isotherm data of PFOA sorption was fitted with both Freundlich and linear models and the latter fitted better. The sorption-desorption of PFOA onto ten soil samples depended on soil organic carbon content and composition of soil minerals. The sorption and desorption isotherms of PFOA on ten soils were linear, except for the sorption of PFOA onto a few soils, which was described by the Freundlich equation with the parameter N >1. The main sorption mechanism of PFOA was hydrophobic interaction between the perfluorinated carbon chain and the organic matter of soil, as evidenced by the correlation between the solid-liquid distribution coefficient and the fraction of soil organic carbon. The sorption of PFOA in soils was highly irreversible. Copyright © 2017 Elsevier Inc. All rights reserved.

Competitive sorption of carbonate and arsenic to hematite: combined ATR-FTIR and batch experiments.

PubMed

Brechbühl, Yves; Christl, Iso; Elzinga, Evert J; Kretzschmar, Ruben

2012-07-01

The competitive sorption of carbonate and arsenic to hematite was investigated in closed-system batch experiments. The experimental conditions covered a pH range of 3-7, arsenate concentrations of 3-300 μM, and arsenite concentrations of 3-200 μM. Dissolved carbonate concentrations were varied by fixing the CO(2) partial pressure at 0.39 (atmospheric), 10, or 100 hPa. Sorption data were modeled with a one-site three plane model considering carbonate and arsenate surface complexes derived from ATR-FTIR spectroscopy analyses. Macroscopic sorption data revealed that in the pH range 3-7, carbonate was a weak competitor for both arsenite and arsenate. The competitive effect of carbonate increased with increasing CO(2) partial pressure and decreasing arsenic concentrations. For arsenate, sorption was reduced by carbonate only at slightly acidic to neutral pH values, whereas arsenite sorption was decreased across the entire pH range. ATR-FTIR spectra indicated the predominant formation of bidentate binuclear inner-sphere surface complexes for both sorbed arsenate and sorbed carbonate. Surface complexation modeling based on the dominant arsenate and carbonate surface complexes indicated by ATR-FTIR and assuming inner-sphere complexation of arsenite successfully described the macroscopic sorption data. Our results imply that in natural arsenic-contaminated systems where iron oxide minerals are important sorbents, dissolved carbonate may increase aqueous arsenite concentrations, but will affect dissolved arsenate concentrations only at neutral to alkaline pH and at very high CO(2) partial pressures. Copyright © 2012 Elsevier Inc. All rights reserved.

Predicting sorption of organic acids to a wide range of carbonized sorbents

NASA Astrophysics Data System (ADS)

Sigmund, Gabriel; Kah, Melanie; Sun, Huichao; Hofmann, Thilo

2016-04-01

Many contaminants and infochemicals are organic acids that undergo dissociation under environmental conditions. The sorption of dissociated anions to biochar and other carbonized sorbents is typically lower than that of neutral species. It is driven by complex processes that are not yet fully understood. It is known that predictive approaches developed for neutral compounds are unlikely to be suitable for organic acids, due to the effects of dissociation on sorption. Previous studies on the sorption of organic acids to soils have demonstrated that log Dow, which describes the decrease in hydrophobicity of acids upon dissociation, is a useful alternative to log Kow. The aim of the present study was to adapt a log Dow based approach to describe the sorption of organic acids to carbonized sorbents. Batch experiments were performed with a series of 9 sorbents (i.e., carbonized wood shavings, pig manure, and sewage sludge, carbon nanotubes and activated carbon), and four acids commonly used for pesticidal and biocidal purposes (i.e., 2,4-D, MCPA, 2,4-DB, and triclosan). Sorbents were comprehensively characterized, including by N2 and CO2 physisorption, Fourier transform infrared spectroscopy, and elemental analysis. The wide range of sorbents considered allows (i) discussing the mechanisms driving the sorption of neutral and anionic species to biochar, and (ii) their dependency on sorbate and sorbent properties. Results showed that the sorption of the four acids was influenced by factors that are usually not considered for neutral compounds (i.e., pH, ionic strength). Dissociation affected the sorption of the four compounds, and sorption of the anions ranged over five orders of magnitude, thus substantially contributing to sorption in some cases. For prediction purposes, most of the variation in sorption to carbonized sorbents (89%) could be well described with a two-parameter regression equation including log Dow and sorbent specific surface area. The proposed model may serve as a base to estimate the environmental fate of organic acids in the presence of carbonized sorbents such as biochar, and help assess (i) the potential application of biochar for remediation purposes and (ii) the potential effect of biochar addition to soil.

Magnetite impregnation effects on the sorbent properties of activated carbons and biochars.

PubMed

Han, Zhantao; Sani, Badruddeen; Mrozik, Wojciech; Obst, Martin; Beckingham, Barbara; Karapanagioti, Hrissi K; Werner, David

2015-03-01

This paper discusses the sorbent properties of magnetic activated carbons and biochars produced by wet impregnation with iron oxides. The sorbents had magnetic susceptibilities consistent with theoretical predictions for carbon-magnetite composites. The high BET surface areas of the activated carbons were preserved in the synthesis, and enhanced for one low surface area biochar by dissolving carbonates. Magnetization decreased the point of zero charge. Organic compound sorption correlated strongly with BET surface areas for the pristine and magnetized materials, while metal cation sorption did not show such a correlation. Strong sorption of the hydrophobic organic contaminant phenanthrene to the activated carbon or biochar surfaces was maintained following magnetite impregnation, while phenol sorption was diminished, probably due to enhanced carbon oxidation. Copper, zinc and lead sorption to the activated carbons and biochars was unchanged or slightly enhanced by the magnetization, and iron oxides also contributed to the composite metal sorption capacity. While a magnetic biochar with 219 ± 3.7 m(2)/g surface area nearly reached the very strong organic pollutant binding capacity of the two magnetic activated carbons, a magnetic biochar with 68 ± 2.8 m(2)/g surface area was the best metal sorbent. Magnetic biochars thus hold promise as more sustainable alternatives to coal-derived magnetic activated carbons. Copyright © 2014 Elsevier Ltd. All rights reserved.

Evaluation of the sorption mechanism of ionic liquids onto multi-walled carbon nanotubes.

PubMed

Wojsławski, Jerzy; Białk-Bielińska, Anna; Paszkiewicz, Monika; Toński, Michał; Stepnowski, Piotr; Dołżonek, Joanna

2018-01-01

The knowledge of the sorption mechanism of different chemicals onto third generation carbon sorbents such as carbon nanotubes (CNTs) is needed in order to project systems for the effective removal of pollutants from the environment. This paper reports evaluation of the sorption mechanism of selected ionic liquids (ILs), being considered as potential pollutant in environment, onto various CNTs. CNTs characterized by the smallest diameter and the biggest surface area showed the highest sorption capacity to isolate ILs from an aqueous solution. CNTs with a bigger diameter, a functionalized surface and particularly a helical shape showed a lower sorption capacity. The sorption mechanism has been defined as complex, including van der Waals, π-π and electrostatic interactions with dominating π-π interactions. Due to the relatively high sorption coefficient (355.98 ± 20.69-6397.10 ± 355.42 L kg -1 depending on the IL) the study showed that multi-walled carbon nanotubes can potentially be used to effectively isolate ILs from an aqueous solution. Moreover, proved in this study, the fast sorption kinetic, and uncomplicated regeneration process, leading to an even higher sorption capacity, means that CNTs are promising material which could find potential applications in the treatment of water contaminated by ILs. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorption of triclosan onto activated carbon, kaolinite and montmorillonite: effects of pH, ionic strength, and humic acid.

PubMed

Behera, Shishir Kumar; Oh, Seok-Young; Park, Hung-Suck

2010-07-15

Sorption of triclosan on three sorbents, viz., activated carbon, kaolinite and montmorillonite was studied as a function of pH, ionic strength and humic acid (HA) concentration through controlled batch experiments. Triclosan sorption was found to be higher in the acidic pH range, as varying pH showed significant influence on the surface charge of the sorbents and degree of ionization of the sorbate. Sorption capacity of the sorbents increased with an increase in the ionic strength of solution. At low pH (pH 3), the overall increase in triclosan sorption was 1.2, approximately 4 and 3.5 times, respectively for activated carbon, kaolinite and montmorillonite when ionic strength was increased from 1x10(-3) to 5x10(-1) M. Triclosan sorption onto activated carbon decreased from 31.4 to 10.6 mg g(-1) by increasing the HA concentration to 200 mg C L(-1). However, during sorption onto kaolinite and montmorillonite, the effect of HA was very complex probably due to (i) hydrophobicity (log K(ow)=4.76) of triclosan; and (ii) complexation of HA with triclosan. Though triclosan sorption onto activated carbon is higher, the potential of kaolinite and montmorillonite in controlling the transport of triclosan in subsurface environment can still be appreciable. 2010 Elsevier B.V. All rights reserved.

Impact of exotic earthworms on organic carbon sorption on mineral surfaces and soil carbon inventories in a northern hardwood forest

Treesearch

Amy Lyttle; Kyungsoo Yoo; Cindy Hale; Anthony Aufdenkampe; Stephen D. Sebestyen; Kathryn Resner; Alex Blum

2015-01-01

Exotic earthworms are invading forests in North America where native earthworms have been absent since the last glaciation. These earthworms bioturbate soils and may enhance physical interactions between minerals and organic matter (OM), thus affecting mineral sorption of carbon (C) which may affect C cycling. We quantitatively show how OM-mineral sorption and soil C...

Assessing soil and groundwater contamination from biofuel spills.

PubMed

Chen, Colin S; Shu, Youn-Yuen; Wu, Suh-Huey; Tien, Chien-Jung

2015-03-01

Future modifications of fuels should include evaluation of the proposed constituents for their potential to damage environmental resources such as the subsurface environment. Batch and column experiments were designed to simulate biofuel spills in the subsurface environment and to evaluate the sorption and desorption behavior of target fuel constituents (i.e., monoaromatic and polyaromatic hydrocarbons) in soil. The extent and reversibility of the sorption of aromatic biofuel constituents onto soil were determined. When the ethanol content in ethanol-blended gasoline exceeded 25%, enhanced desorption of the aromatic constituents to water was observed. However, when biodiesel was added to diesel fuel, the sorption of target compounds was not affected. In addition, when the organic carbon content of the soil was higher, the desorption of target compounds into water was lower. The empirical relationships between the organic-carbon normalized sorption coefficient (Koc) and water solubility and between Koc and the octanol-water partition coefficient (Kow) were established. Column experiments were carried out for the comparison of column effluent concentration/mass from biofuel-contaminated soil. The dissolution of target components depended on chemical properties such as the hydrophobicity and total mass of biofuel. This study provides a basis for predicting the fate and transport of hydrophobic organic compounds in the event of a biofuel spill. The spill scenarios generated can assist in the assessment of biofuel-contaminated sites.

Sorbed atrazine shifts into non-desorbable sites of soil organic matter during aging.

PubMed

Park, Jeong-Hun; Feng, Yucheng; Cho, Sung Yong; Voice, Thomas C; Boyd, Stephen A

2004-11-01

Soil-chemical contact time (aging) is an important determinant of the sorption and desorption characteristics of the organic contaminants and pesticides in the environment. The effects of aging on mechanism-specific sorption and desorption of atrazine were studied in soil and clay slurries. Sorption isotherm and desorption kinetic experiments were performed, and soil-water distribution coefficients and desorption rate parameters were evaluated using linear and non-linear sorption equations and a three-site desorption model, respectively. Aging time for sorption of atrazine in sterilized soil and clay slurries ranged from 2 days to 8 months. Atrazine sorption isotherms were nearly linear (r(2)>0.97) and sorption coefficients were strongly correlated to soil organic carbon content. Sorption distribution coefficients (K(d)) increased with increase in age in all five soils studied, but not for K-montmorillonite. Sorption non-linearity did not increase with increase in age except for the Houghton muck soil. Desorption profiles were well described by the three-site desorption model. The equilibrium site fraction (f(eq)) decreased and the non-desorbable site fraction (f(nd)) increased as a function of aging time in all soils. For K-montmorillonite, f(nd) approximately 0 regardless of aging, showing that aging phenomena are sorbent/mechanism specific. In all soils, it was found that when normalized to soil organic matter content, the concentration of atrazine in desorbable sites was relatively constant, whereas that in non-desorbable site increased. This, and the lack of aging effects on desorption from montmorillonite, suggests that sorption into non-desorbable sites of soil organic matter is primary source of increased atrazine sorption in soils during aging.

Biochar: a green sorbent to sequester acidic organic contaminants

NASA Astrophysics Data System (ADS)

Sigmund, Gabriel; Kah, Melanie; Sun, Huichao; Hofmann, Thilo

2015-04-01

Biochar is a carbon rich product of biomass pyrolysis that exhibits a high sorption potential towards a wide variety of inorganic and organic contaminants. Because it is a valuable soil additive and a potential carbon sink that can be produced from renewable resources, biochar has gained growing attention for the development of more sustainable remediation strategies. A lot of research efforts have been dedicated to the sorption of hydrophobic contaminants and metals to biochar. Conversely, the understanding of the sorption of acidic organic contaminants remains limited, and questions remain on the influence of biochar characteristics (e.g. ash content) on the sorption behaviour of acidic organic contaminants. To address this knowledge gap, sorption batch experiments were conducted with a series of structurally similar acidic organic contaminants covering a range of dissociation constant (2,4-D, MCPA, 2,4-DB and triclosan). The sorbents selected for experimentation included a series of 10 biochars covering a range of characteristics, multiwalled carbon nanotubes as model for pure carbonaceous phases, and an activated carbon as benchmark. Overall, sorption coefficient [L/kg] covered six orders of magnitude and generally followed the order 2,4-D < MCPA < 2,4-DB < triclosan. Combining comprehensive characterization of the sorbents with the sorption dataset allowed the discussion of sorption mechanisms and driving factors of sorption. Statistical analysis suggests that (i) partitioning was the main driver for sorption to sorbents with small specific surface area (< 25 m²/g), whereas (ii) specific mechanisms dominated sorption to sorbents with larger specific surface area. Results showed that factors usually not considered for the sorption of neutral contaminants play an important role for the sorption of organic acids. The pH dependent lipophilicity ratio (i.e. D instead of Kow), ash content and ionic strength are key factors influencing the sorption of acidic organic contaminants to biochars. Overall, the identified factors, as well as the environmental matrix, should be carefully considered when selecting the type of biochar for sequestration purposes.

Adsorption of Ammonia on Regenerable Carbon Sorbents

NASA Technical Reports Server (NTRS)

Wójtowicz, Marek A.; Cosgrove, Jesph E.; Serio, Michael A..; Wilburn, Monique

2015-01-01

Results are presented on the development of reversible sorbents for the combined carbon dioxide, moisture, and trace-contaminant (TC) removal for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). The currently available life support systems use separate units for carbon dioxide, trace contaminants, and moisture control, and the long-term objective is to replace the above three modules with a single one. Data on sorption and desorption of ammonia, which is a major TC of concern, are presented in this paper. The current TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal, which is non-regenerable, and the carbon-based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. In this study, several carbon sorbents were fabricated and tested for ammonia sorption. Ammonia-sorption capacity was related to carbon pore structure characteristics, and the temperature of oxidative carbon-surface treatment was optimized for enhanced ammonia-sorption performance.

Sorption of carbamazepine by commercial graphene oxides: a comparative study with granular activated carbon and multiwalled carbon nanotubes.

PubMed

Cai, Nan; Larese-Casanova, Philip

2014-07-15

Graphene nanosheet materials represent a potentially new high surface area sorbent for the treatment of endocrine disrupting compounds (EDCs) in water. However, sorption behavior has been reported only for laboratory graphene prepared by a laborious and hazardous graphite exfoliation process. A careful examination of commercially available, clean, high-volume produced graphene materials should reveal whether they are appropriate for sorbent technologies and which physicochemical properties most influence sorption performance. In this study, three commercially available graphene oxide powders of various particle sizes, specific surface areas, and surface chemistries were evaluated for their sorption performance using carbamazepine and nine other EDCs and were compared to that of conventional granular activated carbon (GAC) and multi-walled carbon nanotubes (MWCNTs). Sorption kinetics of carbamazepine on graphene oxide powders was rapid and reversible with alcohol washing, consistent with π-π interactions. The various sorption extents as described by Freundlich isotherms were best explained by available surface area, and only the highest surface area graphene oxide (771 m(2)/g) out-performed GAC and MWCNTs. Increasing pH caused more negative surface charge, a twofold decrease in sorption of anionic ibuprofen, a onefold increase in sorption of cationic atenolol, and no change for neutral carbamazepine, highlighting the role of electrostatic interactions. Copyright © 2014 Elsevier Inc. All rights reserved.

Differences in sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid on artificial soils as a function of soil pre-aging.

PubMed

Waldner, Georg; Friesl-Hanl, Wolfgang; Haberhauer, Georg; Gerzabek, Martin H

The sorption behavior of the herbicide 4-chloro-2-methylphenoxyacetic acid (MCPA) to three different artificial soil mixtures was investigated. Artificial soils serve as model systems for improving understanding of sorption phenomena. The soils consisted of quartz, ferrihydrite, illite, montmorillonite, and charcoal. In a previous study, several selected mixtures had been inoculated with organic matter, and microbial aging (incubation) had been performed for different periods of time (3, 12, and 18 months) before conducting the sorption experiments. The effect of this pre-incubation time on the sorption behavior was determined. Interaction of MCPA with soil surfaces was monitored by aqueous phase sorption experiments, using high-performance liquid chromatography/ultraviolet and in selected cases Fourier-transformed infrared spectroscopy. The sorption behavior showed large differences between differently aged soils; Freundlich and linear sorption model fits (with sorption constants K f , 1/ n exponents, and K d values, respectively) were given for pH = 3 and the unbuffered pH of ∼7. The largest extent of sorption from diluted solutions was found on the surfaces with a pre-incubation time of 3 months. Sorption increased at acidic pH values. Regarding the influence of aging of artificial soils, the following conclusions were drawn: young artificial soils exhibit stronger sorption at lower concentrations, with a larger K f value than aged soils. A correlation with organic carbon content was not confirmed. Thus, the sorption characteristics of the soils are more influenced by the aging of the organic carbon than by the organic carbon content itself.

Sorption of perfluorooctane sulfonate and perfluorooctanoate on activated carbons and resin: Kinetic and isotherm study.

PubMed

Yu, Qiang; Zhang, Ruiqi; Deng, Shubo; Huang, Jun; Yu, Gang

2009-03-01

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) have increasingly attracted global concerns in recent years due to their global distribution, persistence, strong bioaccumulation and potential toxicity. The feasibility of using powder activated carbon (PAC), granular activated carbon (GAC) and anion-exchange resin (AI400) to remove PFOS and PFOA from water was investigated with regard to their sorption kinetics and isotherms. Sorption kinetic results show that the adsorbent size influenced greatly the sorption velocity, and both the GAC and AI400 required over 168h to achieve the equilibrium, much longer than 4h for the PAC. Two kinetic models were adopted to describe the experimental data, and the pseudo-second-order model well described the sorption of PFOS and PFOA on the three adsorbents. The sorption isotherms show that the GAC had the lowest sorption capacity both for PFOS and PFOA among the three adsorbents, while the PAC and AI400 possessed the highest sorption capacity of 1.04mmolg(-1) for PFOS and 2.92mmolg(-1) for PFOA according to the Langmuir fitting. Based on the sorption behaviors and the characteristics of the adsorbents and adsorbates, ion exchange and electrostatic interaction as well as hydrophobic interaction were deduced to be involved in the sorption, and some hemi-micelles and micelles possibly formed in the intraparticle pores.

Quantitative high-resolution mapping of phenanthrene sorption to black carbon particles.

PubMed

Obst, Martin; Grathwohl, Peter; Kappler, Andreas; Eibl, Oliver; Peranio, Nicola; Gocht, Tilman

2011-09-01

Sorption of hydrophobic organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) to black carbon (BC) particles has been the focus of numerous studies. Conclusions on sorption mechanisms of PAH on BC were mostly derived from studies of sorption isotherms and sorption kinetics, which are based on batch experiments. However, mechanistic modeling approaches consider processes at the subparticle scale, some including transport within the pore-space or different spatial pore-domains. Direct evidence based on analytical techniques operating at the submicrometer scale for the location of sorption sites and the adsorbed species is lacking. In this work, we identified, quantified, and mapped the sorption of PAHs on different BC particles (activated carbon, charcoal and diesel soot) on a 25-100 nm scale using scanning transmission X-ray microscopy (STXM). In addition, we visualized the pore structure of the particles by transmission electron microscopy (TEM) on the 1-10 nm-scale. The combination of the chemical information from STXM with the physical information from TEM revealed that phenanthrene accumulates in the interconnected pore-system along primary "cracks" in the particles, confirming an adsorption mechanism.

An Impact of Mechanical Stress in Coal Briquettes on Sorption of Carbon Dioxide

NASA Astrophysics Data System (ADS)

Wierzbicki, Mirosław

2017-09-01

The presence of gases (methane or carbon dioxide) in hard coal is connected with numerous threats for miners employed in underground mining facilities. When analyzing the coal-methane system, it is necessary to determine the relationship between pressure and gas sorption. Such a relationship should be determined under conditions similar to the natural ones - when it comes to both temperature and pressure. The present paper discusses the results of research conducted with the use of coal briquettes under the state of mechanical stress. Carbon dioxide sorption isotherms were determined for different values of stress affecting the coal material. For five coal samples collected in different mines of the Upper Silesian Coal Basin, Langmuir's sorption isotherms were determined. The results point to significant impact that mechanical stress has upon the sorption process. It is about 1 percent of the value obtained for coal not subjected to stress per 1 MPa. The research results can also prove useful when analyzing hard coal seams from the perspective of their carbon dioxide sequestration abilities.

Heterogeneous carbonaceous matter in sedimentary rock lithocomponents causes significant trichloroethylene (TCE) sorption in a low organic carbon content aquifer/aquitard system

NASA Astrophysics Data System (ADS)

Choung, Sungwook; Zimmerman, Lisa R.; Allen-King, Richelle M.; Ligouis, Bertrand; Feenstra, Stanley

2014-10-01

This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on trichloroethylene (TCE) sorption for a low fraction organic carbon content (foc) alluvial sedimentary aquifer and aquitard system (foc = 0.046-0.105%). The equilibrium TCE sorption isotherms were highly nonlinear with Freundlich exponents of 0.46-0.58. Kerogen + black carbon was the dominant CM fraction extracted from the sediments and accounted for > 60% and 99% of the total in the sands and silt, respectively. Organic petrological examination determined that the kerogen included abundant amorphous organic matter (bituminite), likely of marine origin. The dark calcareous siltstone exhibited the greatest TCE sorption among aquifer lithocomponents and accounted for most sorption in the aquifer. The results suggest that the source of the thermally altered CM, which causes nonlinear sorption, was derived from parent Paleozoic marine carbonate rocks that outcrop throughout much of New York State. A synthetic aquifer-aquitard unit system (10% aquitard) was used to illustrate the effect of the observed nonlinear sorption on mass storage potential at equilibrium. The calculation showed that > 80% of TCE mass contained in the aquifer was sorbed on the aquifer sediment at aqueous concentration < 1000 μg L- 1. These results show that sorption is likely a significant contributor to the persistence of a TCE groundwater plume in the aquifer studied. It is implied that sorption may similarly contribute to TCE persistence in other glacial alluvial aquifers with similar geologic characteristics, i.e., comprised of sedimentary rock lithocomponents that contain thermally altered CM.

Comparison of high-pressure CO 2 sorption isotherms on Eastern and Western US coals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Romanov, V; Hur, T -B; Fazio, J

2013-10-01

Accurate estimation of carbon dioxide (CO 2) sorption capacity of coal is important for planning the CO 2 sequestration efforts. In this work, we investigated sorption and swelling behavior of several Eastern and Western US coal samples from the Central Appalachian Basin and from San Juan Basin. The CO 2 sorption isotherms have been completed at 55°C for as received and dried samples. The role of mineral components in coal, the coal swelling, the effects of temperature and moisture, and the error propagation have been analyzed. Changes in void volume due to dewatering and other factors such as temporary cagingmore » of carbon dioxide molecules in coal matrix were identified among the main factors affecting accuracy of the carbon dioxide sorption isotherms. The (helium) void volume in the sample cells was measured before and after the sorption isotherm experiments and was used to build the volume-corrected data plots.« less

Sorption and leaching potential of isoproturon and atrazine in low organic carbon soil of Pakistan under a wheat-maize rotation

USDA-ARS?s Scientific Manuscript database

Limited data are available on the sorption and leaching of pesticides in agricultural soils of Pakistan with low soil organic carbon (OC). Sorption potential of two widely used pesticides, isoproturon and atrazine, was determined using the batch equilibration method on soils from 0-35 cm, 35-70 and ...

Experimental study of Pb (II) solution sorption behavior onto Coffee Husk Bioactivated Carbon

NASA Astrophysics Data System (ADS)

Fona, Z.; Habibah, U.

2018-04-01

Coffee husk which is abundantly produced in the coffee plantations is potential to be a challenging adsorbent. The fate of Pb (II) solution in the sorption mechanism onto the adsorbent has been investigated. This paper aimed to study the efficiency of Pb (II) aqueous solution removal using activated carbon from coffee husk (CAC). The sorption characteristics were using two isotherm models, Langmuir and Freundlich, were also reported. The coffee husk from local plantations in Middle Aceh was carbonized and sieved to 120/140 mesh. The charcoal was activated using hydrochloric acid before contacted with the different initial concentrations of Pb (II) solution. The remaining concentrations of the metal in the specified contact times were determined using Atomic Adsorption Spectrophotometer at 283.3 wavelength. The result showed that the equilibrium concentrations were obtained in about 30 minutes which depended on the initial concentration. The sorption mechanism followed Freundlich isotherm model where the adsorption constant and capacity were accordingly 1.353 and 1.195 mgg‑1. The iodine sorption was up to 1,053 mgg‑1. Based on the ash and moisture content, as well as iodine sorption, the activated carbon met the national standard.

Role of structure, accessibility and microporosity on sorption of phenanthrene and nonylphenol by sediments and their fractions.

PubMed

Zhang, Dainan; Duan, Dandan; Huang, Youda; Xiong, Yongqiang; Yang, Yu; Ran, Yong

2016-12-01

To better understand interaction mechanism of sediment organic matter with hydrophobic organic compounds, sorption of phenanthrene (Phen) and nonylphenol (NP) by bulk sediments and their fractions was investigated. Three surface sediments were selectively fractionated into different organic fractions, including the demineralized carbon (DM), lipid free carbon (LF), lipid (LP), and nonhydrolyzable carbon (NHC) fractions. The structure and microporosity of the isolated fractions were characterized by NMR and CO 2 adsorption techniques, and used as sorbents for Phen and NP. The calculated micropore volumes (V o ) and specific surface area (SSA) values are positively related to the concentrations of aromatic C and char for the DM, LF and NHC fractions, suggesting that aromatic moieties and char component significantly contribute to the microporosity. The LF fractions exhibit greater sorption affinity than the DM fractions do, indicating that the presence of LP could block the accessibility of sorption sites for Phen and NP. Significant and positive correlations among log K' FOC values for Phen and NP and aromatic carbon and char contents, and V o and SSA values suggest the aromatic moieties and microporosity dominate their sorption of HOCs by sediment organic matter (SOM). As the NHC fractions have much stronger sorption than other fractions do, they dominate the overall sorption by the bulk samples. This study indicated that the important roles of aromatic moieties, accessibility, and microporosity in the sorption of HOCs by SOM. Copyright © 2016 Elsevier Ltd. All rights reserved.

CEC-normalized clay-water sorption isotherm

NASA Astrophysics Data System (ADS)

Woodruff, W. F.; Revil, A.

2011-11-01

A normalized clay-water isotherm model based on BET theory and describing the sorption and desorption of the bound water in clays, sand-clay mixtures, and shales is presented. Clay-water sorption isotherms (sorption and desorption) of clayey materials are normalized by their cation exchange capacity (CEC) accounting for a correction factor depending on the type of counterion sorbed on the mineral surface in the so-called Stern layer. With such normalizations, all the data collapse into two master curves, one for sorption and one for desorption, independent of the clay mineralogy, crystallographic considerations, and bound cation type; therefore, neglecting the true heterogeneity of water sorption/desorption in smectite. The two master curves show the general hysteretic behavior of the capillary pressure curve at low relative humidity (below 70%). The model is validated against several data sets obtained from the literature comprising a broad range of clay types and clay mineralogies. The CEC values, derived by inverting the sorption/adsorption curves using a Markov chain Monte Carlo approach, are consistent with the CEC associated with the clay mineralogy.

SORPTION OF VOLATILE ORGANIC SOLVENTS FROM AQUEOUS SOLUTION ONTO SUBSURFACE SOLIDS

EPA Science Inventory

Sorption isotherms for tetrachloroethene on low-carbon subsurface core samples were linear to equilibrium solution concentrations of 2 mg L−1. Concentrations above this value produced pronounced curvature in the sorption isotherms. Sorption of tetrachloroethene, benzene, trichlor...

Processes and kinetics of Cd2+ sorption by a calcareous aquifer sand

USGS Publications Warehouse

Fuller, C.C.; Davis, J.A.

1987-01-01

The rate of Cd2+ sorption by a calcareous aquifer sand was characterized by two reaction steps, with the first step reaching completion in 24 hours. The second step proceeded at a slow and nearly constant rate for at least seven days. The first step includes a fast adsorption reaction which is followed by diffusive transport into either a disordered surface film of hydrated calcium carbonate or into pore spaces. After 24 hours the rate of Cd2+ sorption was constant and controlled by the rate of surface coprecipitation, as a solid solution of CdCO3 in CaCO3 formed in recrystallizing material. Desorption of Cd2+ from the sand was slow. Clean grains of primary minerals, e.g. quartz and aluminosilicates. sorbed much less Cd2+ than grains which had surface patches of secondary minerals, e.g. carbonates, iron and manganese oxides. Calcite grains sorbed the greatest amount of Cd2+ on a weight-normalized basis despite the greater abundance of quartz. A method is illustrated for determining empirical binding constants for trace metals at in situ pH values without introducing the experimental problem of supersaturation. The binding constants are useful for solute transport models which include a computation of aqueous speciation. ?? 1987.

Assessment of herbicide sorption by biochars and organic matter associated with soil and sediment

USDA-ARS?s Scientific Manuscript database

Sorption of two herbicides, fluridone (FLUN) and norflurazon (NORO), by whole sediment, two types of biochars and various soil/sediment organic matter (OM) fractions including nonhydrolyzable carbon (NHC), black carbon (BC) and humic acid (HA) was examined. The single-point organic carbon (OC)-norma...

Strong sorption of PCBs to nanoplastics, microplastics, carbon nanotubes, and fullerenes.

PubMed

Velzeboer, I; Kwadijk, C J A F; Koelmans, A A

2014-05-06

The presence of microplastic and carbon-based nanoparticles in the environment may have implications for the fate and effects of traditional hydrophobic chemicals. Here we present parameters for the sorption of 17 CB congeners to 10-180 μm sized polyethylene (micro-PE), 70 nm polystyrene (nano-PS), multiwalled carbon nanotubes (MWCNT), fullerene (C60), and a natural sediment in the environmentally relevant 10(-5)-10(-1) μg L(-1) concentration range. Effects of salinity and sediment organic matter fouling were assessed by measuring the isotherms in fresh- and seawater, with and without sediment present. Sorption to the "bulk" sorbents sediment organic matter (OM) and micro-PE occurred through linear hydrophobic partitioning with OM and micro-PE having similar sorption affinity. Sorption to MWCNT and nano-PS was nonlinear. PCB sorption to MWCNT and C60 was 3-4 orders of magnitude stronger than to OM and micro-PE. Sorption to nano-PS was 1-2 orders of magnitude stronger than to micro-PE, which was attributed to the higher aromaticity and surface-volume ratio of nano-PS. Organic matter effects varied among sorbents, with the largest OM fouling effect observed for the high surface sorbents MWCNT and nano-PS. Salinity decreased sorption for sediment and MWCNT but increased sorption for the polymers nano-PS and micro-PE. The exceptionally strong sorption of (planar) PCBs to C60, MWCNT, and nano-PS may imply increased hazards upon membrane transfer of these particles.

Method and apparatus for separating gases based on electrically and magnetically enhanced monolithic carbon fiber composite sorbents

DOEpatents

Judkins, Roddie R.; Burchell, Timothy D.

1999-01-01

A method for separating gases or other fluids involves placing a magnetic field on a monolithic carbon fiber composite sorption material to more preferentially attract certain gases or other fluids to the sorption material to which a magnetic field is applied. This technique may be combined with the known "pressure swing adsorption" technique utilizing the same sorption material.

Heterogeneous carbonaceous matter in sedimentary rock lithocomponents causes significant trichloroethylene (TCE) sorption in a low organic carbon content aquifer/aquitard system.

PubMed

Choung, Sungwook; Zimmerman, Lisa R; Allen-King, Richelle M; Ligouis, Bertrand; Feenstra, Stanley

2014-10-15

This study evaluated the effects of heterogeneous thermally altered carbonaceous matter (CM) on trichloroethylene (TCE) sorption for a low fraction organic carbon content (foc) alluvial sedimentary aquifer and aquitard system (foc=0.046-0.105%). The equilibrium TCE sorption isotherms were highly nonlinear with Freundlich exponents of 0.46-0.58. Kerogen+black carbon was the dominant CM fraction extracted from the sediments and accounted for >60% and 99% of the total in the sands and silt, respectively. Organic petrological examination determined that the kerogen included abundant amorphous organic matter (bituminite), likely of marine origin. The dark calcareous siltstone exhibited the greatest TCE sorption among aquifer lithocomponents and accounted for most sorption in the aquifer. The results suggest that the source of the thermally altered CM, which causes nonlinear sorption, was derived from parent Paleozoic marine carbonate rocks that outcrop throughout much of New York State. A synthetic aquifer-aquitard unit system (10% aquitard) was used to illustrate the effect of the observed nonlinear sorption on mass storage potential at equilibrium. The calculation showed that >80% of TCE mass contained in the aquifer was sorbed on the aquifer sediment at aqueous concentration <1000 μgL(-1). These results show that sorption is likely a significant contributor to the persistence of a TCE groundwater plume in the aquifer studied. It is implied that sorption may similarly contribute to TCE persistence in other glacial alluvial aquifers with similar geologic characteristics, i.e., comprised of sedimentary rock lithocomponents that contain thermally altered CM. Copyright © 2014 Elsevier B.V. All rights reserved.

[Adsorption behavior and influence factors of p-nitroaniline on high surface area activated carbons prepared from plant stems].

PubMed

Li, Kun-quan; Zheng, Zheng; Luo, Xing-zhang

2010-08-01

Low-cost and high surface area microporous activated carbons were prepared from Spartina alternilora and cotton stalk with KOH activation under the conditions of impregnation ratio of 3.0, activation temperature at 800 degrees C and activation time of 1.5 h. The adsorption behavior of p-nitroaniline on the activated carbons was investigated by batch sorption experiments. The influences of solution pH value, adsorbent dose and temperature were investigated. The adsorption isotherm and thermodynamic characteristics were also discussed. The Spartina alterniflora activated carbon (SA-AC) has a high surface area of 2825 m2 x g(-1) and a micropore volume of 1.192 cm3 x g(-1). The BET surface area and micropore volume of the cotton stalk activated carbon (CS-AC) are 2135 m2 x g(-1) and 1.011 cm3 x g(-1), respectively. The sorption experiments show that both the activated carbons have high sorption capacity for p-nitroaniline. The Langmuir maximum sorption amount was found to be 719 mg x g(-1) for SA-AC and 716 mg x g(-1) for CS-AC, respectively. The sorption was found to depend on solution pH, adsorbent dose, and temperature. The optimum pH for the removal of p-nitroaniline was found to be 7.0. The Freundlich model and Redlich-Peterson model can describe the experimental data effectively. The negative changes in free energy (delta G0) and enthalpy (delta H0) indicate that the sorption is a spontaneous and exothermic procedure. The negative values of the adsorption entropy delta S0 indicate that the mobility of p-nitroaniline on the carbon surface becomes more restricted as compared with that of those in solution.

Method and apparatus for separating gases based on electrically and magnetically enhanced monolithic carbon fiber composite sorbents

DOEpatents

Judkins, R.R.; Burchell, T.D.

1999-07-20

A method for separating gases or other fluids involves placing a magnetic field on a monolithic carbon fiber composite sorption material to more preferentially attract certain gases or other fluids to the sorption material to which a magnetic field is applied. This technique may be combined with the known pressure swing adsorption'' technique utilizing the same sorption material. 1 fig.

Sorption of thiabendazole in sub-tropical Brazilian soils.

PubMed

de Oliveira Neto, Odilon França; Arenas, Alejandro Yopasa; Fostier, Anne Hélène

2017-07-01

Thiabendazole (TBZ) is an ionizable anthelmintic agent that belongs to the class of benzimidazoles. It is widely used in veterinary medicine and as a fungicide in agriculture. Sorption and desorption are important processes influencing transport, transformation, and bioavailability of xenobiotic compounds in soils; data related to sorption capacity are therefore needed for environmental risk assessments. The aim of this work was to assess the sorption potential of TBZ in four Brazilians soils (sandy, sandy-clay, and clay soils), using batch equilibrium experiments at three pH ranges (2.3-3.0, 3.8-4.2, and 5.5-5.7). The Freundlich sorption coefficient (K F ) ranged from 9.0 to 58 μg 1-1/n  (mL) 1/n  g -1 , with higher values generally observed at the lower pH ranges (2.3-3.0 and 3.8-4.2) and for clay soils. The highest organic carbon-normalized sorption coefficients (K OC ) obtained at pH 3.8-5.7 (around the natural pH range of 4.1-5.0) for both clay soils and sandy-clay soil were 3255 and 2015 mL g -1 , respectively. The highest correlations K F vs SOM (r = 0.70) and K F vs clay content (r = 0.91) were observed at pH 3.8-4.2. Our results suggest that TBZ sorption/desorption is strongly pH dependent and that its mobility could be higher in the studied soils than previously reported in soils from temperate regions.

Comparison of tetrachloromethane sorption to an alkylammonium-clay and an alkyldiammonium-clay

USGS Publications Warehouse

Smith, J.A.; Jaffe, P.R.

1991-01-01

The interlamellar space of Wyoming bentonite (clay) was modified by exchanging either decyltrimethyl-ammonium (DTMA) or decyltrimethyldiammonium (DTMDA) cations for inorganic ions, and tetrachloromethane sorption to the resulting two organoclays from water was studied at 10, 20, and 35??C. Only one end of the 10-carbon alkyl chain of the DTMA cation is attached to the silica surface of the clay mineral, and tetrachloromethane sorption of DTMA-clay is characterized by isotherm linearity, noncompetitive sorption, weak solute uptake, and a relatively low heat of sorption. Both ends of the 10-carbon chain of the DTMDA cation are attached to the silica surface of the clay mineral, and tetrachloromethane sorption to DTMDA-clay is characterized by nonlinear isotherms, competitive sorption, strong solute uptake, and a relatively high, exothermic heat of sorption that varies as a function of the mass of tetrachloromethane sorbed. Therefore, the attachment of both ends of the alkyl chain to the interlamellar mineral surface appears to change the sorption mechanism from a partition-dominated process to an adsorption-dominated process. ?? 1991 American Chemical Society.

Reactive mineral removal relative to soil organic matter heterogeneity and implications for organic contaminant sorption.

PubMed

Li, Fangfang; Pan, Bo; Liang, Ni; Chang, Zhaofeng; Zhou, Yuwei; Wang, Lin; Li, Hao; Xing, Baoshan

2017-08-01

Soil organic matter (SOM) is generally treated as a static compartment of soil in pollutant fate studies. However, SOM might be altered or fractionated in soil systems, and the details of SOM property/composition changes when coupled with contaminant behavior are unknown. In this study, a mild acid treatment was adopted to remove reactive minerals and partially remove SOM components. After acid treatment, biomarker signatures showed that lignin-derived phenols were released and black carbon (as suggested by benzene-polycarboxylic acids) and lipids were enriched. The biomarker information was consistent with common bulk chemical characterization. The sorption coefficient K d for PHE was two times higher after acid treatment, whereas K d for OFL was three times lower. The organic carbon normalized sorption coefficient K OC values for PHE were higher for soils after acid treatment, indicating stronger interactions between PHE and SOM. The linear regression line between K d and f OC for OFL showed lower intercepts and slopes after reactive mineral removal, suggesting a decreased contribution of minerals and reduced dependence on SOM. These results were attributed to the release of polar compositions in SOM accompanied by reactive mineral removal. Our results suggest that the mobility of ionic organic contaminants increases, whereas that of hydrophobic organic contaminants decreases after acid treatment with respect to reactive mineral depletion. This study emphasized that new insights into the coupling of SOM dynamics should be incorporated into organic contaminant behavior studies. SOM molecular biomarkers offer a useful technique for correlating SOM composition and sorption property changes. Copyright © 2017 Elsevier Ltd. All rights reserved.

Potential phosphorus eutrophication mitigation strategy: Biochar carbon composition, thermal stability and pH influence phosphorus sorption.

PubMed

Ngatia, L W; Hsieh, Y P; Nemours, D; Fu, R; Taylor, R W

2017-08-01

Phosphorus (P) eutrophication is a major pollution problem globally, with unprecedented amount of P emanating from agricultural sources. But little is known about the optimization of soil-biochar P sorption capacity. The study objective was to determine how biochar feedstocks and pyrolysis conditions influences carbon (C) thermal stability, C composition and pH and in turn influence the phosphorus sorption optimization. Biochar was produced from switchgrass, kudzu and Chinese tallow at 200, 300, 400, 500, 550, 650,750 °C. Carbon thermal stability was determined by multi-element scanning thermal analysis (MESTA), C composition was determined using solid state 13 C NMR. Phosphorus sorption was determined using a mixture of 10% biochar and 90% sandy soil after incubation. Results indicate increased P sorption (P < 0.0001) and decreased P availability (P < 0.0001) with increasing biochar pyrolysis temperature. However, optimum P sorption was feedstock specific with switchgrass indicating P desorption between 200 and 550 °C. Phosphorus sorption was in the order of kudzu > switchgrass > Chinese tallow. Total C, C thermal stability, aromatic C and alkalinity increased with elevated pyrolysis temperature. Biochar alkalinity favored P sorption. There was a positive relationship between high thermal stable C and P sorption for Kudzu (r = 0.62; P = 0.0346) and Chinese tallow (r = 0.73; P = 0.0138). In conclusion, biochar has potential for P eutrophication mitigation, however, optimum biochar pyrolysis temperature for P sorption is feedstock specific and in some cases might be out of 300-500 °C temperature range commonly used for agronomic application. High thermal stable C dominated by aromatic C and alkaline pH seem to favor P sorption. Copyright © 2017 Elsevier Ltd. All rights reserved.

Kinetics of sorption of polyaromatic hydrocarbons onto granular activated carbon and Macronet hyper-cross-linked polymers (MN200).

PubMed

Valderrama, C; Cortina, J L; Farran, A; Gamisans, X; Lao, C

2007-06-01

Polymeric supports are presented as an alternative to granular activated carbon (GAC) for organic contaminant removal from groundwater using permeable reactive barriers (PRB). The search for suitable polymeric sorbents for hydrocarbon extraction from aqueous streams has prompted the synthesis of new resins incorporating new functionalities or modifying the polymer network properties that solve many of the existing problems. Between them, the new type of polymeric sorbents Macronet Hypersol containing a styrene-divinylbenzene macroporous hyperreticulated network has been evaluated. Because of their potential sorptive properties, tests were conducted to determine the feasibility of using them as a low-cost reactive material for groundwater applications. The present work describes the sorption of six polycyclic hydrocarbons (PAHs) from aqueous solution onto both Macronet polymeric sorbent MN200 and granular activated carbon. Batch experiments were performed to determine loading rates of a family of PAHs (naphthalene, fluorene, anthracene, acenaphthene, pyrene, and fluoranthene), from a simple two-rings PAH (naphthalene) up to a four-ring PAH (pyrene). The behavior of a non-functionalized Macronet support (MN200) was compared with the behavior of a recognized material, granular activated carbon (GAC). Analyses of the respective rate data with three theoretical models (pseudo-first- and pseudo-second-order reaction models and the Elovich model) were used to describe the PAH sorption kinetics. Sorption rate constants were determined by graphical analysis of the proposed models. The study showed that sorption systems followed a pseudo-first-order reaction model, although the pseudo-second-order reaction model provides an acceptable description of the sorption process. Graphical analysis showed that the sorption process with activated carbon is a more complex process than the one observed for hyper-cross-linked polymers (MN200). A simulation of the barrier thickness needed to treat a PAH-polluted plume showed that 0.1-1 m of sorption media is enough even for high water fluxes such as 0.1-2 m(3)/m(2)/day for both sorbents.

Phosphorus sorption on marine carbonate sediment: phosphonate as model organic compounds.

PubMed

Huang, Xiao-Lan; Zhang, Jia-Zhong

2011-11-01

Organophosphonate, characterized by the presence of a stable, covalent, carbon to phosphorus (C-P) bond, is a group of synthetic or biogenic organophosphorus compounds. The fate of these organic phosphorus compounds in the environment is not well studied. This study presents the first investigation on the sorption of phosphorus (P) in the presence of two model phosphonate compounds, 2-aminothylphosphonoic acid (2-AEP) and phosphonoformic acid (PFA), on marine carbonate sediments. In contrast to other organic P compounds, no significant inorganic phosphate exchange was observed in seawater. P was found to adsorb on the sediment only in the presence of PFA, not 2-AEP. This indicated that sorption of P from phosphonate on marine sediment was compound specific. Compared with inorganic phosphate sorption on the same sediments, P sorption from organic phosphorus is much less in the marine environment. Further study is needed to understand the potential role of the organophosphonate compounds in biogeochemical cycle of phosphorus in the environment. Copyright © 2011 Elsevier Ltd. All rights reserved.

Adsorptive removal of direct azo dye from aqueous phase onto coal based sorbents: a kinetic and mechanistic study.

PubMed

Venkata Mohan, S; Chandrasekhar Rao, N; Karthikeyan, J

2002-03-01

This communication presents the results pertaining to the investigation conducted on color removal of trisazo direct dye, C.I. Direct Brown 1:1 by adsorption onto coal based sorbents viz. charfines, lignite coal, bituminous coal and comparing results with activated carbon (Filtrasorb-400). The kinetic sorption data indicated the sorption capacity of the different coal based sorbents. The sorption interaction of direct dye on to coal based sorbents obeys first-order irreversible rate equation and activated carbon fits with the first-order reversible rate equation. Intraparticle diffusion studies revealed the dye sorption interaction was complex and intraparticle diffusion was not only the rate limiting step. Isothermal data fit well with the rearranged Langmuir adsorption model. R(L) factor revealed the favorable nature of the isotherm of the dye-coal system. Neutral solution pH yielded maximum dye color removal. Desorption and interruption studies further indicated that the coal based sorbents facilitated chemisorption in the process of dye sorption while, activated carbon resulted in physisorption interaction.

Sorption of ionizable and ionic organic compounds to biochar, activated carbon and other carbonaceous materials.

PubMed

Kah, Melanie; Sigmund, Gabriel; Xiao, Feng; Hofmann, Thilo

2017-11-01

The sorption of ionic and ionizable organic compounds (IOCs) (e.g., pharmaceuticals and pesticides) on carbonaceous materials plays an important role in governing the fate, transport and bioavailability of IOCs. The paradigms previously established for the sorption of neutral organic compounds do not always apply to IOCs and the importance of accounting for the particular sorption behavior of IOCs is being increasingly recognized. This review presents the current state of knowledge and summarizes the recent advances on the sorption of IOCs to carbonaceous sorbents. A broad range of sorbents were considered to evaluate the possibility to read across between fields of research that are often considered in isolation (e.g., carbon nanotubes, graphene, biochar, and activated carbon). Mechanisms relevant to IOCs sorption on carbonaceous sorbents are discussed and critically evaluated, with special attention being given to emerging sorption mechanisms including low-barrier, charge-assisted hydrogen bonds and cation-π assisted π-π interactions. The key role played by some environmental factors is also discussed, with a particular focus on pH and ionic strength. Overall the review reveals significant advances in our understanding of the interactions between IOCs and carbonaceous sorbents. In addition, knowledge gaps are identified and priorities for future research are suggested. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of surface oxides on the adsorption of naphthalene onto multiwalled carbon nanotubes.

PubMed

Cho, Hyun-Hee; Smith, Billy A; Wnuk, Joshua D; Fairbrother, D Howard; Ball, William P

2008-04-15

As greater quantities of carbon nanotubes (CNTs) enter the environment, they will have an increasingly important effect on the availability and transport of aqueous contaminants. As a consequence of purification, deliberate surface functionalization, and/or exposure to oxidizing agents after release to the environment, CNTs often contain surface oxides (i.e., oxygen containing functional groups). To probe the influence that surface oxides exert on CNT sorption properties, multiwalled CNTs (MWCNTs) with varying oxygen concentrations were studied with respect to their sorption properties toward naphthalene. For pristine (as-received) MWCNTs, the sorption capacity was intermediate between that of a natural char and a granular activated carbon. Sorption data also reveal that a linear relationship exists between the oxygen content of MWCNTs and their maximum adsorption capacity for naphthalene, with 10% surface oxygen concentration resulting in a roughly 70% decrease in maximum adsorption capacity. The relative distribution of sorption energies, as characterized by Freundlich isotherm exponents was, however, unaffected by oxidation. Thus, the data are consistent with the idea that incorporated surface oxides create polar regions that reduce the surface area available for naphthalene sorption. These results highlight the important role of surface chemistry in controlling the environmental properties of CNTs.

Adsorptive removal of phthalate ester (Di-ethyl phthalate) from aqueous phase by activated carbon: a kinetic study.

PubMed

Venkata Mohan, S; Shailaja, S; Rama Krishna, M; Sarma, P N

2007-07-19

Adsorptive studies were carried out on Di-ethyl phthalate (DEP) removal from aqueous phase onto activated carbon. Batch sorption studies were performed and the results revealed that activated carbon demonstrated ability to adsorb DEP. Influence of varying experimental conditions such as DEP concentration, pH of aqueous solution, and dosage of adsorbent were investigated on the adsorption process. Sorption interaction of DEP onto activated carbon obeyed the pseudo second order rate equation. Experimental data showed good fit with both the Langmuir and Freundlich adsorption isotherm models. DEP sorption was found to be dependent on the aqueous phase pH and the uptake was observed to be greater at acidic pH.

Co-Adsorption of Ammonia and Formaldehyde on Regenerable Carbon Sorbents for the Primary Life Support System (PLSS)

NASA Technical Reports Server (NTRS)

Wojtowicz, Marek A.; Cosgrove, Joseph E.; Serio, Michael A.; Wilburn, Monique S.

2016-01-01

Results are presented on the development of a reversible carbon sorbent for trace-contaminant (TC) removal for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). The current TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal, which is deemed non-regenerable, while the carbon-based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. Data on concurrent sorption and desorption of ammonia and formaldehyde, which are major TCs of concern, are presented in this paper. A carbon sorbent was fabricated by dry impregnation of a reticulated carbon-foam support with polyvinylidene chloride, followed by carbonization and thermal oxidation in air. Sorbent performance was tested for ammonia and formaldehyde sorption and vacuum regeneration, with and without water present in the gas stream. It was found that humidity in the gas phase enhanced ammonia-sorption capacity by a factor larger than two. Co-adsorption of ammonia and formaldehyde in the presence of water resulted in strong formaldehyde sorption (to the point that it was difficult to saturate the sorbent on the time scales used in this study). In the absence of humidity, adsorption of formaldehyde on the carbon surface was found to impair ammonia sorption in subsequent runs; in the presence of water, however, both ammonia and formaldehyde could be efficiently removed from the gas phase by the sorbent. The efficiency of vacuum regeneration could be enhanced by gentle heating to temperatures below 60 deg.

Isolation and characterization of biochar-derived organic matter fractions and their phenanthrene sorption.

PubMed

Jin, Jie; Sun, Ke; Liu, Wei; Li, Shiwei; Peng, Xianqiang; Yang, Yan; Han, Lanfang; Du, Ziwen; Wang, Xiangke

2018-05-01

Chemical composition and pollutant sorption of biochar-derived organic matter fractions (BDOMs) are critical for understanding the long-term environmental significance of biochar. Phenanthrene (PHE) sorption by the humic acid-like (HAL) fractions isolated from plant straw- (PLABs) and animal manure-based (ANIBs) biochars, and the residue materials (RES) after HAL extraction was investigated. The HAL fraction comprised approximately 50% of organic carbon (OC) of the original biochars. Results of XPS and 13 C NMR demonstrated that the biochar-derived HAL fractions mainly consisted of aromatic clusters substituted by carboxylic groups. The CO 2 cumulative surface area of BDOMs excluding PLAB-derived RES fractions was obviously lower than that of corresponding biochars. The sorption nonlinearity of PHE by the fresh biochars was significantly stronger than that of the BDOM fractions, implying that the BDOM fractions were more chemically homogeneous. The BDOMs generally exhibited comparable or higher OC-normalized distribution coefficients (K oc ) of PHE than the original biochars. The PHE logK oc values of the fresh biochars correlated negatively with the micropore volumes due to steric hindrance effect. In contrast, a positive relationship between the sorption coefficients (K d ) of BDOMs and the micropore volumes was observed in this study, suggesting that pore filling could dominate PHE sorption by the BDOMs. The positive correlation between the PHE logK oc values of the HAL fractions and the aromatic C contents indicates that PHE sorption by the HAL fractions was regulated by aromatic domains. The findings of this study improve our knowledge of the evolution of biochar properties after application and its potential environmental impacts. Copyright © 2018 Elsevier Ltd. All rights reserved.

Robust Means for Estimating Black Carbon-Water Sorption Coefficients of Organic Contaminants in Sediments

DTIC Science & Technology

2015-07-01

multiple lines of reasoning should be used to build confidence in what we believe is going on at any particular site. Hence, it will certainly be more...site depends on its Kd value (Fernandez et al., 2009). Consequently, we need to understand factors that go into the Kd sorption parameter in order...models of sorption to GAC (Kamlet et al. 1985, Luehrs et al. 1996, Poole and Poole 1997, Shih and Gschwend 2009) and multi-walled carbon nanotubes ( MWCNT

The sorption of influenza viruses and antibiotics on carbon nanotubes and polyaniline nanocomposites

NASA Astrophysics Data System (ADS)

Ivanova, V. T.; Katrukha, G. S.; Timofeeva, A. V.; Ilyna, M. V.; Kurochkina, Y. E.; Baratova, L. A.; Sapurina, I. Yu; Ivanov, V. F.

2011-04-01

The decontamination of the solutions from micropatogens and drug delivery are the important problems of modern life. It was shown that carbon nanotubes, polyaniline and their composites can interact with antibiotics-polypeptides and some viruses (pandemic strain of influenza viruses A(H1N1)v circulated in Russia in 2009-2010. During a short time drug and viruses can be absorbed by polyaniline and removed from aqueous solutions at the normal conditions. Polyaniline composites can be useful for the preparation of drug delivery and virus control filters and also in biotechnology for the improvement the methods of antibiotics purification.

Nature of the interlayer environment in an organoclay optimized for the sequestration of dibenzo-p-dioxin.

PubMed

Johnston, Cliff T; Khan, Bushra; Barth, Edwin F; Chattopadhyay, Sandip; Boyd, Stephen A

2012-09-04

A Na-smectite clay (Na-SWy-2) was exchanged with various amounts of dimethyldioctadecylammonium bromide (DODA-Br) up to twice the cation exchange capacity (CEC). The organoclay (DODA-SWy-2) with DODA-Br added at 2 × CEC exhibited a maximum 4.2 nm d-spacing and a 31.4% carbon content, which demonstrates DODA(+) intercalation. DODA-SWy-2 was evaluated as an archetype of commercial products used to sequester hydrophobic contaminants, and the nature of the primarily C18 alkylhydrocarbon-chain interlayer environment was emhasized. Shifts in ν(CH) and CH(2) rocking band positions in DODA-SWy-2-complex FTIR-spectra indicate that DODA C18 chains were more ordered as DODA surface coverage was increased. Differential scanning calorimetry analysis indicated a DODA-SWy-2 gel-to-liquid transition temperature much lower than the melting point of crystalline DODA-Br and similar to that of aqueous DODA-Br vesicles. This suggests that the transition was governed by C18 alkyl tail-tail interactions in the clay interlamellar region. Dibenzo-p-dioxin (DD) sorption from water by DODA-SWy-2 was compared to DD sorption by the geosorbents granular activated carbon (GAC), K-exchanged saponite, and a muck soil. The linear K(l) sorption coefficients (log K(l)) from a linear fit of the sorption isotherms were 4.37 for DODA-SWy-2, 5.55 for GAC, 3.19 for muck soil, and 2.46 for K-saponite. The DD-organic-matter-normalized sorption coefficient (K(om)) was ∼2.4 times the octanol-water partition coefficient (K(ow)). This indicates that DD has a higher affinity for the nonpolar interlayer DODA organic phase than for octanol. In contrast, the K(om) for muck soil DD sorption was ~10 times less than K(ow), which reflects the higher polarity of amorphous soil organic matter relative to octanol. Enhanced DD uptake by the DODA-derived lipophilic phase in the organoclay is attributed to the low polarity, "open" C18 alkyl structure due to the physical dimensions of "v-shaped" DODA(+) molecular, and low density of the interlamellar phase (~0.50 g/cm3) density of intercalated DODA(+).

Nature of the Interlayer Environment in an Organoclay Optimized for the Sequestration of Dibenzo-p-dioxin

PubMed Central

Johnston, Cliff T.; Khan, Bushra; Barth, Edwin F.; Chattopadhyay, Sandip; Boyd, Stephen A.

2015-01-01

A Na–smectite clay (Na–SWy-2) was exchanged with various amounts of dimethyldioctadecylammonium bromide (DODA-Br) up to twice the cation exchange capacity (CEC). The organoclay (DODA–SWy-2) with DODA-Br added at 2 × CEC exhibited a maximum 4.2 nm d-spacing and a 31.4% carbon content, which demonstrates DODA+ intercalation. DODA–SWy-2 was evaluated as an archetype of commercial products used to sequester hydrophobic contaminants, and the nature of the primarily C18 alkylhydrocarbon-chain interlayer environment was emhasized. Shifts in ν(CH) and CH2 rocking band positions in DODA–SWy-2-complex FTIR-spectra indicate that DODA C18 chains were more ordered as DODA surface coverage was increased. Differential scanning calorimetry analysis indicated a DODA–SWy-2 gel-to-liquid transition temperature much lower than the melting point of crystalline DODA-Br and similar to that of aqueous DODA-Br vesicles. This suggests that the transition was governed by C18 alkyl tail–tail interactions in the clay interlamellar region. Dibenzo-p-dioxin (DD) sorption from water by DODA–SWy-2 was compared to DD sorption by the geosorbents granular activated carbon (GAC), K-exchanged saponite, and a muck soil. The linear Kl sorption coefficients (log Kl) from a linear fit of the sorption isotherms were 4.37 for DODA–SWy-2, 5.55 for GAC, 3.19 for muck soil, and 2.46 for K-saponite. The DD-organic-matter-normalized sorption coefficient (Kom) was ~2.4 times the octanol–water partition coefficient (Kow). This indicates that DD has a higher affinity for the nonpolar interlayer DODA organic phase than for octanol. In contrast, the Kom for muck soil DD sorption was ~10 times less than Kow, which reflects the higher polarity of amorphous soil organic matter relative to octanol. Enhanced DD uptake by the DODA-derived lipophilic phase in the organoclay is attributed to the low polarity, “open” C18 alkyl structure due to the physical dimensions of “v-shaped” DODA+ molecular, and low density of the interlamellar phase (~0.50 g/ cm3) density of intercalated DODA+. PMID:22856528

Strong binding of apolar hydrophobic organic contaminants by dissolved black carbon released from biochar: A mechanism of pseudomicelle partition and environmental implications.

PubMed

Fu, Heyun; Wei, Chenhui; Qu, Xiaolei; Li, Hui; Zhu, Dongqiang

2018-01-01

Dissolved black carbon (DBC), the soluble fraction of black carbon (BC), is an important constituent of dissolved organic matter pool. However, little is known about the binding interactions between hydrophobic organic contaminants (HOCs) and DBC and their significance in the fate process. This study determined the binding ability of DBC released from rice-derived BC for a series of apolar HOCs, including four polycyclic aromatic hydrocarbons and four chlorinated benzenes, using batch sorption and solubility enhancement techniques. Bulk BC and a dissolved soil humic acid (DSHA) were included as benchmark sorbents. The organic carbon-normalized sorption coefficient of phenanthrene to DBC was slightly lower than bulk BC, but was over ten folds higher than DSHA. Consistently, DBC was more effective than DSHA in enhancing the apparent water solubility of the tested HOCs, and the enhancement positively correlated with solute n-octanol-water partition coefficient, indicating the predominance of hydrophobic partition. The much higher binding ability of DBC relative to DSHA was mainly attributed to its higher tendency to form pseudomicellar structures as supported by the fluorescence quenching and the pH-edge data. Our findings suggest that DBC might play a significant role in the environmental fate and transport of HOCs as both sorbent and carrier. Copyright © 2017 Elsevier Ltd. All rights reserved.

Structures for capturing CO.sub.2, methods of making the structures, and methods of capturing CO.sub.2

DOEpatents

Jones, Christopher W; Hicks, Jason C; Fauth, Daniel J; McMahan, Gray

2012-10-30

Briefly described, embodiments of this disclosure, among others, include carbon dioxide (CO.sub.2) sorption structures, methods of making CO.sub.2 sorption structures, and methods of using CO.sub.2 sorption structures.

Enhanced sorption of PAHs in natural-fire-impacted sediments from Oriole Lake, California.

PubMed

Sullivan, Julia; Bollinger, Kevyn; Caprio, Anthony; Cantwell, Mark; Appleby, Peter; King, John; Ligouis, Bertrand; Lohmann, Rainer

2011-04-01

Surface sediment cores from Oriole Lake (CA) were analyzed for organic carbon (OC), black carbon (BC), and their δ(13)C isotope ratios. Sediments displayed high OC (20-25%) and increasing BC concentrations from ∼0.40% (in 1800 C.E.) to ∼0.60% dry weight (in 2000 C.E.). Petrographic analysis confirmed the presence of fire-derived carbonaceous particles/BC at ∼2% of total OC. Natural fires were the most likely cause of both elevated polycyclic aromatic hydrocarbon (PAH) concentrations and enhanced sorption in Oriole Lake sediments prior to 1850, consistent with their tree-ring-based fire history. In contrast to other PAHs, retene and perylene displayed decreasing concentrations during periods with natural fires, questioning their use as fire tracers. The occurrence of natural fires, however, did not result in elevated concentrations of black carbon or chars in the sediments. Only the 1912-2007 sediment layer contained anthropogenic particles, such as soot BC. In this layer, combining OC absorption with adsorption to soot BC (using a Freundlich coefficient n = 0.7) explained the observed sorption well. In the older layers, n needed to be 0.3 and 0.5 to explain the enhanced sorption to the sediments, indicating the importance of natural chars/inertinites in sorbing PAHs. For phenanthrene, values of n differed significantly between sorption to natural chars (0.1-0.4) and sorption to anthropogenic black carbon (>0.5), suggesting it could serve as an in situ probe of sorbents.

Sorption of perfluorooctanoic acid, perfluorooctane sulfonate and perfluoroheptanoic acid on granular activated carbon.

PubMed

Zhang, Di; Luo, Qi; Gao, Bin; Chiang, Sheau-Yun Dora; Woodward, David; Huang, Qingguo

2016-02-01

The sorption of perfluorooctane sulfonate (PFOS), perfluorooctanoic acid (PFOA), and perfluoroheptanoic acid (PFHpA) on granular activated carbon (GAC) was characterized and compared to explore the underlying mechanisms. Sorption of the three perfluoroalkyl acids (PFAAs) on GAC appeared to be a rapid intra-particle diffusion process, which were well represented by the pseudo-second-order rate model with the sorption rate following the order PFOS > PFOA > PFHpA. Sorption isotherm data were well fitted by the Freundlich model with the sorption capacity (Kf) of PFOS, PFOA and PFHpA being 4.45, 2.42 and 1.66 respectively. This suggests that the hydrophilic head group on PFAAs, i.e. sulfonate vs carboxylic, has a strong influence on their sorption. Comparison between PFOA and PFHpA revealed that hydrophobicity could also play a role in the sorption of PFAAs on GAC when the fluorocarbon chain length is different. Analyses using Attenuated Total Reflection (ATR)-Fourier Transform Infrared (FTIR) spectroscopy suggested possible formation of a negative charge-assisted H-bond between PFAAs and the functionalities on GAC surfaces, including non-aromatic ketones, sulfides, and halogenated hydrocarbons. Copyright © 2015 Elsevier Ltd. All rights reserved.

Using polyacrylate-coated SPME fibers to quantify sorption of polar and ionic organic contaminants to dissolved organic carbon.

PubMed

Haftka, Joris J-H; Scherpenisse, Peter; Jonker, Michiel T O; Hermens, Joop L M

2013-05-07

A passive sampling method using polyacrylate-coated solid-phase microextraction (SPME) fibers was applied to determine sorption of polar and ionic organic contaminants to dissolved organic carbon (DOC). The tested contaminants included pharmaceuticals, industrial chemicals, hormones, and pesticides and represented neutral, anionic, and cationic structures. Prior to the passive sampler application, sorption of the chemicals to the fibers was characterized. This was needed in order to accurately translate concentrations measured in fibers to freely dissolved aqueous concentrations during the sorption tests with DOC. Sorption isotherms of neutral compounds to the fiber were linear, whereas isotherms of basic chemicals covered a nonlinear and a linear range. Sorption of acidic and basic compounds to the fiber was pH-dependent and was dominated by sorption of the neutral sorbate species. Fiber- and DOC-water partition coefficients of neutral compounds were both linearly related to octanol-water partition coefficients (log Kow). The results of this study show that polyacrylate fibers can be used to quantify sorption to DOC of neutral and ionic contaminants, having multiple functional groups and spanning a wide hydrophobicity range (log Kow = 2.5-7.5).

Characteristics and influencing factors of tetrachloroethylene sorption-desorption on soil and its components.

PubMed

Qiu, Zhaofu; Yang, Weiwei; He, Long; Zhao, Zhexuan; Lu, Shuguang; Sui, Qian

2016-02-01

To investigate the effects of soil structure, soil organic carbon (SOC), minerals, initial tetrachloroethylene (PCE) concentration (C0), and ionic strength (Ci) on PCE sorption-desorption, six types of soil were adopted as adsorbents, including two types of natural soil and four types of soil with most of the "soft carbon" pre-treated by H2O2 or with all SOC removed from the original soil by 600 °C ignition. The results showed that all of the sorption-desorption isotherms of PCE were non-linear within the experimental range, and the H2O2-treated samples exhibited higher non-linear sorption isotherms than those of the original soils. The hysteresis index of PCE sorption to original soil is less pronounced than that of the H2O2-treated and 600 °C-heated samples due to the entrapment of sorbate molecules in the "hard carbon" domain, together with the meso- and microporous structures within the 600 °C-heated samples. Both SOC and minerals have impacts on the sorption-desorption of PCE, and the sorption-desorption contribution rate of minerals increased with decreasing SOC content. C0 has almost no influence on the sorption to minerals of the soils, but the contribution rate of minerals decreased with increasing C0 in the desorption stage. As a result of the salting-out effect, PCE sorption capacity was increased by increasing Ci, especially when Ci ≥ 0.1 M. Moreover, desorption increased and hysteresis weakened with increasing Ci, except for the 600 °C-heated samples. In addition, no significant effect of Ci on desorption of PCE and no hysteresis was observed in this experimental range for the 600 °C-heated samples. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

PubMed

Zhang, Weihua; Huang, Xinchen; Jia, Yanming; Rees, Frederic; Tsang, Daniel C W; Qiu, Rongliang; Wang, Hong

2017-04-01

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 (Al 2 O 3 ). 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 Al 2 O 3 , indicating the significance of temperature-dependent diffusion processes in SDBC and AC. Nevertheless, metal sorption was more selective on Al 2 O 3 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.

From carbon nanostructures to high-performance sorbents for chromatographic separation and preconcentration

NASA Astrophysics Data System (ADS)

Postnov, V. N.; Rodinkov, O. V.; Moskvin, L. N.; Novikov, A. G.; Bugaichenko, A. S.; Krokhina, O. A.

2016-02-01

Information on carbon nanostructures (fullerenes, nanotubes, graphene, nanodiamond and nanodispersed active carbon) used to develop high-performance sorbents of organics and heavy metal ions from aqueous solutions is collected and analyzed. The advantages in the synthesis of hybrid carbon nanostructures and the possibilities of surface modification of these systems in order to carry out fast sorption pre-concentration are considered. Prospects for application of these materials in sorption technologies and analytical chemistry are discussed. The bibliography includes 364 references.

The Influence of Hydrophilic Interactions on the Sorption and Mobility of Naproxen at Environmentally-Relevant Concentrations

NASA Astrophysics Data System (ADS)

Muller, K.; Ramsburg, C. A.

2011-12-01

Managed underground storage of reclaimed wastewater is currently one viable option for meeting increasing demands on water resources, yet the attenuation of many emerging contaminants within the subsurface environment is not well understood. Pharmaceuticals are of particular concern due to the rapid increase in development and use of these compounds, observations of incomplete removal during wastewater treatment, and emerging concerns over ecosystem effects. Assessment of the subsurface attenuation of pharmaceuticals is difficult because the compounds are polar, pH-active, and present at low-concentration (ng/L). Predictions of sorption that only consider hydrophobic interactions with soil organic matter may not fully describe the extent to which reversible sequestration influences pharmaceutical attenuation. In fact, hydrophilic interactions (i.e. ion exchange, cation-induced sorption, hydrogen bonding, etc) may represent important contributions to total sorption, especially when aqueous solutes are present at low concentration. Here we assess the sorption of naproxen - an acidic pharmaceutical - to three subsurface materials using equilibrium batch experiments and 1-d column experiments. Subsurface materials evaluated include Ottawa sand (quartz with negligible organic carbon and negligible iron oxide), Aplite sand (quartz and feldspar with negligible organic carbon, 0.2% wt iron oxide), and a Hinckley series silty-sand (quartz and feldspar with 0.95% wt organic carbon, and 0.4% wt iron oxides). Sorption of naproxen to the Ottawa sand was negligible and did not result in measurable retardation when naproxen was introduced to the porous medium at a concentration of 275 ng/L. Batch experiments suggest that Aplite sand offers quantifiable interaction (52% of the mass introduced is associated with the solid phase when the aqueous concentration is 1000 ng/L and the solid to liquid ratio is 1.4:1 v/v); however, column data are indicative of markedly less interaction and retardation. Naproxen sorption to the Hinckley series material was considerable (99% of the mass introduced is associated with the solid phase when the aqueous concentration is 1000 ng/L and the solid to liquid ratio is 1:1 v/v). Predictions of naproxen sorption based upon the fraction of organic carbon and the organic-carbon partitioning coefficient (Koc) greatly underestimated the sorption observed in all experiments conducted with the Hinckley series material. Assessment of sorption under 1 mM NaH2PO4 (a sorbant with a strong affinity for hydrophilic sites) suggests that hydrophobic interactions account for approximately 45% of the total interaction. Breakthrough of naproxen (C0 ~ 20 ug/L) was substantially retarded in experiments conducted with the Hinckley material and a thermally-treated Hinckley material (negligible organic carbon). These results highlight the potential role of hydrophilic interactions during the transport and attenuation of acidic pharmaceuticals at solute concentrations typical of water reuse applications.

New evidence for high sorption capacity of hydrochar for hydrophobic organic pollutants

USDA-ARS?s Scientific Manuscript database

This study investigated the sorption potential of hydrochars, produced from hydrothermally carbonizing livestock wastes, towards organic pollutants (OPs) with a wide range of hydrophobicity, and compared their sorption capacity with that of pyrochars obtained from conventional dry pyrolysis from the...

Sorption of atrazine and ametryn by carbonatic and non-carbonatic soils of varied origin.

PubMed

Kasozi, G N; Nkedi-Kizza, P; Li, Y; Zimmerman, A R

2012-10-01

Sorption of two s-triazines, atrazine and ametryn, by carbonatic soils, Histosols, Spodosols and Oxisols was examined. Linear isotherms were observed and sorption coefficients (K(d)) of both compounds were significantly lower (α = 0.05) onto carbonatic soils compared to non-carbonatic soils. Furthermore, among carbonatic soil types, the marl-carbonatic soils had the lowest sorption affinities. K(d) and organic carbon content were highly correlated, suggesting predominant influence of organic carbon in the sorption of the s-triazine, except in Oxisols and Spodosols where variations suggest other factors. Upon removal of organic matter (OM) using sodium hypochlorite and hydrogen peroxide, the K(d) values were reduced by ~90%, indicating minimal contribution of mineral surfaces. Thus OM compositional differences likely explain the large variation in s-triazine sorption within and between soil orders. This study highlights the need to consider OM composition in addition to quantity when determining pesticide applications rates, particularly for carbonatic soils. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sorption Behavior of Compressed CO2 and CH4 on Ultrathin Hybrid Poly(POSS-imide) Layers.

PubMed

Raaijmakers, Michiel J T; Ogieglo, Wojciech; Wiese, Martin; Wessling, Matthias; Nijmeijer, Arian; Benes, Nieck E

2015-12-09

Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally accompanied by dilation, or swelling, of the polymer material. In turn, this dilation can result in penetrant induced plasticization and physical aging that affect the nonequilibrium status of the polymer. Here, we investigate the dilation and sorption behavior of ultrathin membrane layers of a hybrid inorganic-organic network material that consists of alternating polyhedral oligomeric silsesquioxane and imide groups, upon exposure to compressed carbon dioxide and methane. The imide precursor contains fluoroalkene groups that provide affinity toward carbon dioxide, while the octa-functionalized silsesquioxane provides a high degree of cross-linking. This combination allows for extremely high sorption capacities, while structural rearrangements of the network are hindered. We study the simultaneous uptake of gases and dilation of the thin films at high pressures using spectroscopic ellipsometry measurements. Ellipsometry provides the changes in both the refractive index and the film thickness, and allows for accurate quantification of sorption and swelling. In contrast, gravimetric and volumetric measurements only provide a single parameter; this does not allow an accurate correction for, for instance, the changes in buoyancy because of the extensive geometrical changes of highly swelling films. The sorption behavior of the ultrathin hybrid layers depends on the fluoroalkene group content. At low pressure, the apparent molar volume of the gases is low compared to the liquid molar volume of carbon dioxide and methane, respectively. At high gas concentrations in the polymer film, the apparent molar volume of carbon dioxide and methane exceeds that of the liquid molar volume, and approaches that of the gas phase. The high sorption capacity and reversible dilation characteristics of the presented materials provide new directions for applications including gas sensors and gas separation membranes.

Carbon Sorption Cryogenic Regenerator

NASA Technical Reports Server (NTRS)

Jones, Jack A.; Petrick, S. Walter; Britcliffe, Michael J.

1989-01-01

Liquid-helium refrigerator includes regenerator filled with carbon sorbent made from Saran polyvinylidene chloride. Material results in lower operating temperatures and longer times between maintenance than comparable refrigerators containing other regenerators. Sorbent material machined to various configurations to fit inside cylindrical regenerator can. Configuration chosen with regard to heat capacity, pressure drop, and rate of sorption.

Kinetic and Isotherm Modelling of the Adsorption of
Phenolic Compounds from Olive Mill Wastewater onto Activated Carbon

PubMed Central

Casazza, Alessandro A.; Perego, Patrizia

2015-01-01

Summary The adsorption of phenolic compounds from olive oil wastewater by commercial activated carbon was studied as a function of adsorbent quantity and temperature. The sorption kinetics and the equilibrium isotherms were evaluated. Under optimum conditions (8 g of activated carbon per 100 mL), the maximum sorption capacity of activated carbon expressed as mg of caffeic acid equivalent per g of activated carbon was 35.8 at 10 °C, 35.4 at 25 °C and 36.1 at 40 °C. The pseudo-second-order model was considered as the most suitable for kinetic results, and Langmuir isotherm was chosen to better describe the sorption system. The results confirmed the efficiency of activated carbon to remove almost all phenolic compound fractions from olive mill effluent. The preliminary results obtained will be used in future studies. The carbohydrate fraction of this upgraded residue could be employed to produce bioethanol, and adsorbed phenolic compounds can be recovered and used in different industries. PMID:27904350

Results of a European interlaboratory comparison on CO2 sorption on activated carbon and coals

NASA Astrophysics Data System (ADS)

Gensterblum, Yves; Busch, Andreas; Krooss, Bernhard; de Weireld, Guy; Billemont, Pierre; van Hemert, Patrick; Wolf, Karl-Heinz

2013-04-01

For the assessment of CO2 storage in coal seams or enhanced coalbed methane production (ECBM), the sorption properties of natural coals are important parameters. Since more and more laboratories worldwide are concerned with measurements of gas sorption on coal it is indispensable to establish quality standards for such experiments. The first two interlaboratory studies on CO2 sorption on coal (Goodman et al. 2004, 2007) revealed a poor agreement of sorption isotherms among the participating laboratories, particularly in the high-pressure range. During the MOVECBM (http://www.movecbm.eu/) project funded by the European Commission (6th framework), an interlaboratory comparison of CO2 sorption on selected coals and activated carbon was initiated. Measurements were performed on dry samples at 45° C using the manometric and the gravimetric method. up to a final pressure of 15 MPa. The first set of high-pressure sorption measurements was performed on a Filtrasorb 400 activated carbon sample in order to minimise heterogeneity effects and to optimize the experimental procedures for the individual (manometric or gravimetric) methods (Gensterblum et al. 2009). Since comparability for the activated carbon was excellent, the measurements were continued using natural coals of various rank (anthracite, bituminous coal and lignite) to study the influence of heterogeneities and varying starting conditions on the CO2 sorption properties (Gensterblum et al. 2010). Compared to the poor reproducibility observed in previous interlaboratory studies (Goodman et al., 2004, 2007) this European study showed excellent agreement (<5 % deviation) among the participating laboratories with good repeatability. The sorption data and technical information on the different experimental setups have been used to investigate errors and potential pitfalls in the assessment of high-pressure CO2 sorption isotherms. References Gensterblum Y., P. van Hemert, P. Billemont, A. Busch, B.M. Krooss, G. de Weireld, D. Prinz , K.-H.A.A. Wolf, "European inter-laboratory comparison of high pressure CO2 sorption isotherms. II: natural coals" IJCG, 2010, 84, 115-124 Gensterblum Y., P. van Hemert, P. Billemont, A. Busch, D. Charriére, D. Li, B.M. Krooss, G. de Weireld, D. Prinz , K.-H.A.A. Wolf, "European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon" Carbon 47 ( 2009 ) 2958 -2969 Goodman, A.L., Busch, A., Duffy, G., Fitzgerald, J.E., Gasem, K.A.M., Gensterblum, Y., Krooss, B.M., Levy, J., Ozdemir, E., Pan, Z., Robinson, Jr., R.L., Schroeder, K., Sudibandriyo, M., White, C. (2004). An Inter-laboratory Comparison of CO2 Isotherms Measured on Argonne Premium Coal Samples. Energy and Fuels 18, 1175-1182. Goodman, A.L., Busch, A., Day, S., Duffy, G.J., Fitzgerald, J.E., Gasem, K.A.M., Gensterblum, Y., Hartman, C., Krooss, B.M., Pan, Z., Pratt, T., Robinson, Jr., R.L., Romanov, V., Sakurovs, R., Schroeder, K., Sudibandriyo, M., White, C.M. (2007) "Inter-laboratory Comparison II: CO2 Isotherms Measured on Moisture-Equilibrated Argonne Premium Coals at 55oC and 15 MPa", International Journal of Coal Geology 72, 153-164.

Uranium and Cesium sorption to bentonite colloids in high salinity and carbonate-rich environments: Implications for radionuclide transport

NASA Astrophysics Data System (ADS)

Tran, E. L.; Teutsch, N.; Klein-BenDavid, O.; Weisbrod, N.

2017-12-01

When radionuclides are leaked into the subsurface due to engineered waste disposal container failure, the ultimate barrier to migration of radionuclides into local aquifers is sorption to the surrounding rock matrix and sediments, which often includes a bentonite backfill. The extent of this sorption is dependent on pH, ionic strength, surface area availability, radionuclide concentration, surface mineral composition, and solution chemistry. Colloidal-sized bentonite particles eroded from the backfill have been shown to facilitate the transport of radionuclides sorbed to them away from their source. Thus, sorption of radionuclides such as uranium and cesium to bentonite surfaces can be both a mobilization or retardation factor. Though numerous studies have been conducted to-date on sorption of radionuclides under low ionic strength and carbonate-poor conditions, there has been little research conducted on the behavior of radionuclides in high salinities and carbonate rich conditions typical of aquifers in the vicinity of some potential nuclear repositories. This study attempts to characterize the sorption properties of U(VI) and Cs to bentonite colloids under these conditions using controlled batch experiments. Results indicated that U(VI) undergoes little to no sorption to bentonite colloids in a high-salinity (TDS= 9000 mg/L) artificial groundwater. This lack of sorption was attributed to the formation of CaUO2(CO3)22- and Ca2UO2(CO3)3 aqueous ions which stabilize the UO22+ ions in solution. In contrast, Cs exhibited greater sorption, the extent to which was influenced greatly by the matrix water's ionic strength and the colloid concentration used. Surprisingly, when both U and Cs were together, the presence of U(VI) in solution decreased Cs sorption, possibly due to the formation of stabilizing CaUO2(CO3)22- anions. The implications of this research are that rather than undergoing colloid-facilitated transport, U(VI) is expected to migrate similarly to a conservative dissolved species under these conditions, and little retardation through sorption onto the surrounding rock matrix is predicted. Cs is expected to undergo more sorption, though U(VI) presence may have a mobilizing effect.

The influence of black carbon on the sorption and desorption of two model PAHs in natural soils.

PubMed

Chi, Fung-Hwa

2014-01-01

Black carbons (BC) which result from the incomplete combustion of farm waste [man-made (burned) BC] are highly absorbent. In Taiwan, the burning of farm waste known as slash and burn is common. The BCs from the burning may present an environmental challenge. Little is known about the effect of BCs on the transport of hydrophobic organic contaminants (HOC). This study investigates the sorption of anthracene and naphthalene to BCs in soil and efficiency of the surfactants Tween 80 and Triton X-100 in their removal. Both surfactants demonstrated 2-6 times increased solubility in the soils with the addiction of BC. Column experiments were performed to imitate the transportation of these contaminants in groundwater through soils before and after adding BC produced by burning farm waste in the lab. We found significantly increased sorption of anthracene in soil added with BCs produced in the lab, suggesting that fraction of organic carbon (foc) can contribute to sorption of such HOCs. Sorption of naphthalene was increased but not significantly. Comparing the concentrations of contaminants, we found the soil containing BC from burned farm waste absorbed HOC more efficiently than the organic BC (naturally-occurring) in the original soil. Therefore, sorption capacity and influence on the transport of HOC cannot be estimated simply by the foc of the soil because the two BCs differ greatly in their sorption ability. BC from farm waste absorbs more contaminants than naturally occurring BC in the soil.

Sorption Behavior of Dye Compounds onto Natural Sediment of Qinghe River.

PubMed

Liu, Ruixia; Liu, Xingmin; Tang, Hongxiao; Su, Yongbo

2001-07-15

The objective of this study is to assess the adsorption behavior of C.I. Basic Yellow X-5GL, C.I. Basic Red 13, C.I. Direct Blue 86, C.I. Vat Yellow 2, and C.I. Mordant Black 11 on natural sediment and to identify sediment characteristics that play a predominant role in the adsorption of the dyes. The potentiometric titration experiment is used to investigate acid-base properties of the sediment surface with a constant capacitance surface complexation model. The parameters controlling the sorption such as solution pH and ion strength, as well as the influence of organic carbon and Ca(2+) ion on the adsorption, are evaluated. It is shown that the titration data can be successfully described by the surface protonation and deprotonation model with the least-squares FITEQL program 2.0. The sorption isotherm data are fitted to the Freundlich equation in a nonlinear form (1/n=0.3-0.9) for all tested dyes. With increasing pH value, the sorption of C.I. Mordant Black 11 and C.I. Direct Blue 86 on the sediment decreases, while for C.I. Basic Yellow X-5GL and C.I. Basic Red 13, the extent of sorption slightly increases. In addition, ion strength also exhibits a considerably different effect on the sorption behavior of these dye compounds. The addition of Ca(2+) can greatly reduce the sorption of C.I. Basic Red 13 on the sediment surface, while it enhances the sorption of C.I. Direct Blue 6. The removal of organic carbon decreases the sorption of C.I. Mordant Black 11 and C.I. Direct Blue 86. In contrast, the sorption of C.I. Basic Red 13 and C.I. Basic Yellow X-5GL is obviously enhanced after the removal of organic carbon. The differences in adsorption behavior are mainly attributed to the physicochemical properties of these dye compounds. Copyright 2001 Academic Press.

Pharmaceuticals' sorptions relative to properties of thirteen different soils.

PubMed

Kodešová, Radka; Grabic, Roman; Kočárek, Martin; Klement, Aleš; Golovko, Oksana; Fér, Miroslav; Nikodem, Antonín; Jakšík, Ondřej

2015-04-01

Transport of human and veterinary pharmaceuticals in soils and consequent ground-water contamination are influenced by many factors, including compound sorption on soil particles. Here we evaluate the sorption isotherms for 7 pharmaceuticals on 13 soils, described by Freundlich equations, and assess the impact of soil properties on various pharmaceuticals' sorption on soils. Sorption of ionizable pharmaceuticals was, in many cases, highly affected by soil pH. The sorption coefficient of sulfamethoxazole was negatively correlated to soil pH, and thus positively related to hydrolytic acidity and exchangeable acidity. Sorption coefficients for clindamycin and clarithromycin were positively related to soil pH and thus negatively related to hydrolytic acidity and exchangeable acidity, and positively related to base cation saturation. The sorption coefficients for the remaining pharmaceuticals (trimethoprim, metoprolol, atenolol, and carbamazepine) were also positively correlated with the base cation saturation and cation exchange capacity. Positive correlations between sorption coefficients and clay content were found for clindamycin, clarithromycin, atenolol, and metoprolol. Positive correlations between sorption coefficients and organic carbon content were obtained for trimethoprim and carbamazepine. Pedotransfer rules for predicting sorption coefficients of various pharmaceuticals included hydrolytic acidity (sulfamethoxazole), organic carbon content (trimethoprimand carbamazepine), base cation saturation (atenolol and metoprolol), exchangeable acidity and clay content (clindamycin), and soil active pH and clay content (clarithromycin). Pedotransfer rules, predicting the Freundlich sorption coefficients, could be applied for prediction of pharmaceutical mobility in soils with similar soil properties. Predicted sorption coefficients together with pharmaceutical half-lives and other imputes (e.g., soil-hydraulic, geological, hydro-geological, climatic) may be used for assessing potential ground-water contamination. Copyright © 2014 Elsevier B.V. All rights reserved.

Dissolved organic matter and estrogen interactions regulate estrogen removal in the aqueous environment: A review.

PubMed

Ma, Li; Yates, Scott R

2018-06-03

This review summarizes the characterization and quantification of interactions between dissolved organic matter (DOM) and estrogens as well as the effects of DOM on aquatic estrogen removal. DOM interacts with estrogens via binding or sorption mechanisms like π-π interaction and hydrogen bonding. The binding affinity is evaluated in terms of organic-carbon-normalized sorption coefficient (Log K OC ) which varies with types and composition of DOM. DOM has been suggested to be a more efficient sorbent compared with other matrices, such as suspended particulate matter, sediment and soil; likely associated with its large surface area and concentrated carbon content. As a photosensitizer, DOM enhanced estrogen photodegradation when the concentration of DOM was below a threshold value, and when above, the acceleration effect was not observed. DOM played a dual role in affecting biodegradation of estrogens depending on the recalcitrance of the DOM and the nutrition status of the degraders. DOM also acted as an electron shuttle (redox mediator) mediating the degradation of estrogens. DOM hindered enzyme-catalyzed removal of estrogens while enhanced their transformation during the simultaneous photo-enzymatic process. Membrane rejection of estrogens was pronounced for hydrophobic DOM with high aromaticity and phenolic moiety content. Elimination of estrogens via photolysis, biodegradation, enzymolysis and membrane rejection in the presence of DOM is initiated by sorption, accentuating the role of DOM as a mediator in regulating aquatic estrogen removal. Published by Elsevier B.V.

Sorption-desorption of fipronil in some soils, as influenced by ionic strength, pH and temperature.

PubMed

Singh, Anand; Srivastava, Anjana; Srivastava, Prakash C

2016-08-01

The sorption-desorpion of fipronil insecticide is influenced by soil properties and variables such as pH, ionic strength, temperature, etc. A better understanding of soil properties and these variables in sorption-desorption processes by quantification of fipronil using liquid chromatography may help to optimise suitable soil management to reduce contamination of surface and groundwaters. In the present investigation, the sorption-desorption of fipronil was studied in some soils at varying concentrations, ionic strengths, temperatures and pH values, and IR specta of fipronil sorbed onto soils were studied. The sorption of fipronil onto soils conformed to the Freundlich isotherm model. The sorption-desorption of fipronil varied with ionic strength in each of the soils. Sorption decreased but desorption increased with temperature. Sorption did not change with increasing pH, but for desorption there was no correlation. The cumulative desorption of fipronil from soil was significantly and inversely related to soil organic carbon content. IR spectra of sorbed fipronil showed the involvement of amino, nitrile, sulfone, chloro and fluoro groups and the pyrazole nucleus of the fipronil molecule. The sorption of fipronil onto soils appeared to be a physical process with the involvement of hydrogen bonding. An increase in soil organic carbon may help to reduce desorption of fipronil. High-temperature regimes are more conducive to the desorption. © 2015 Society of Chemical Industry. © 2015 Society of Chemical Industry.

Comparison of neptunium sorption results using batch and column techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Triay, I.R.; Furlano, A.C.; Weaver, S.C.

1996-08-01

We used crushed-rock columns to study the sorption retardation of neptunium by zeolitic, devitrified, and vitric tuffs typical of those at the site of the potential high-level nuclear waste repository at Yucca Mountain, Nevada. We used two sodium bicarbonate waters (groundwater from Well J-13 at the site and water prepared to simulate groundwater from Well UE-25p No. 1) under oxidizing conditions. It was found that values of the sorption distribution coefficient, Kd, obtained from these column experiments under flowing conditions, regardless of the water or the water velocity used, agreed well with those obtained earlier from batch sorption experiments undermore » static conditions. The batch sorption distribution coefficient can be used to predict the arrival time for neptunium eluted through the columns. On the other hand, the elution curves showed dispersivity, which implies that neptunium sorption in these tuffs may be nonlinear, irreversible, or noninstantaneous. As a result, use of a batch sorption distribution coefficient to calculate neptunium transport through Yucca Mountain tuffs would yield conservative values for neptunium release from the site. We also noted that neptunium (present as the anionic neptunyl carbonate complex) never eluted prior to tritiated water, which implies that charge exclusion does not appear to exclude neptunium from the tuff pores. The column experiments corroborated the trends observed in batch sorption experiments: neptunium sorption onto devitrified and vitric tuffs is minimal and sorption onto zeolitic tuffs decreases as the amount of sodium and bicarbonate/carbonate in the water increases.« less

Production of activated carbon from biodiesel solid residues: An alternative for hazardous metal sorption from aqueous solution.

PubMed

Ribeiro, Rita F L; Soares, Vitor C; Costa, Letícia M; Nascentes, Clésia C

2015-10-01

In this study, the potential for the sorption of Pb(2+) and Cd(2+) from aqueous solutions using HNO3-treated activated carbon (TAC) obtained from radish press cake (Raphanus sativus L.), a solid residue from biodiesel production, was investigated. Activated carbon (AC) was obtained by physical activation with CO2(g). Chemical modification with HNO3 was employed to increase the sorption capability of the AC. The sorption of Pb(2+) and Cd(2+) was studied in monometallic systems in equilibrium with different metal-ion concentrations (10-400 mg L(-1)). The experimental sorption equilibrium data were fit to the Langmuir and Freundlich isotherm models. The maximum sorption capacity (qmax) obtained for AC from the Langmuir isotherm was 45.5 mg g(-1) for Cd(2+) and 250 mg g(-1) for Pb(2+). Moreover, TAC presented qmax of 166.7 mg g(-1) (1.48 mmol g(-1)) for Cd(2+) and 500.0 mg g(-1) (2.41 mmol g(-1)) for Pb(2+)showing the effect of chemical modification. Sorption-desorption studies showed that the interaction between metals and TAC is reversible and this sorbent can be reused for several consecutive cycles. Furthermore, the sorption of Cd(2+) and Pb(2+) by TAC was not affected by the presence of competing ions. The experimental data obtained in this study indicated that this solid residue is viable for the production of sorbents that remove metals, such as cadmium and lead, from wastewaters and thereby contribute to the sustainable development of the production of biodiesel. Copyright © 2015 Elsevier Ltd. All rights reserved.

Effects of pH and anions on the sorption of selenium ions onto magnetite.

PubMed

Kim, Seung Soo; Min, Je Ho; Lee, Jae Kwang; Baik, Min Hoon; Choi, Jong-Won; Shin, Hyung Seon

2012-02-01

This study analyzes the influence of carbonate and silicate, which are generally abundant in granitic groundwater, on the sorption of selenium ions onto magnetite in order to understand the behaviors of selenium in a radioactive waste repository. Selenite was sorbed onto magnetite very well below pH 10, but silicate and carbonate hindered the sorption of selenite onto magnetite. On the other hand, little selenate was sorbed onto magnetite in neutral and weak alkaline solutions of 0.02 M NaNO(3) or NaClO(4), matching the ionic strength in a granitic groundwater, even though silicate or carbonate was not contained in the solutions. The surface complexation constants between selenite and magnetite were obtained by using a geochemical program, FITEQL 4.0, from the experimental data, and the formation of an inner-sphere surface complex such as =FeOSeO(2)(-) was suggested for the sorption of selenite onto magnetite from the diffuse double layer model calculation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Selective Sorption of Dissolved Organic Carbon Compounds by Temperate Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jagadamma, Sindhu; Mayes, Melanie; Phillips, Jana Randolph

Physico-chemical sorption of dissolved organic carbon (DOC) on soil minerals is one of the major processes of organic carbon (OC) stabilization in soils, especially in deeper layers. The attachment of C on soil solids is related to the reactivity of the soil minerals and the chemistry of the sorbate functional groups, but the sorption studies conducted without controlling microbial activity may overestimate the sorption potential of soil. This study was conducted to examine the sorptive characteristics of a diverse functional groups of simple OC compounds (D-glucose, L-alanine, oxalic acid, salicylic acid, and sinapyl alcohol) on temperate climate soil orders (Mollisols,more » Ultisols and Alfisols) with and without biological degradative processes. Equilibrium batch experiments were conducted using 0-100 mg C L-1 at a solid-solution ratio of 1:60 for 48 hrs and the sorption parameters were calculated by Langmuir model fitting. The amount of added compounds that remained in the solution phase was detected by high performance liquid chromatography (HPLC) and total organic C (TOC) analysis. Soil sterilization was performed by -irradiation technique and experiments were repeated to determine the contribution of microbial degradation to apparent sorption. Overall, Ultisols did not show a marked preference for apparent sorption of any of the model compounds, as indicated by a narrower range of maximum sorption capacity (Smax) of 173-527 mg kg soil-1 across compounds. Mollisols exhibited a strong preference for apparent sorption of oxalic acid (Smax of 5290 mg kg soil-1) and sinapyl alcohol (Smax of 2031 mg kg soil-1) over the other compounds. The propensity for sorption of oxalic acid is mainly attributed to the precipitation of insoluble Ca-oxalate due to the calcareous nature of most Mollisol subsoils and its preference for sinapyl alcohol could be linked to the polymerization of this lignin monomer on 2:2 mineral dominated soils. The reactivity of Alfisols to DOC was in between that of Ultisols and Mollisols. HPLC results revealed significantly higher sorption of D-glucose and L-alanine than did TOC results, and duplicate experiments with sterilized soils confirmed that glucose and alanine were mineralized leading to higher apparent sorption values via HPLC. This study demonstrated that three common temperate soil orders experienced differential sorption of simple OC compounds, indicating that sorbate chemistry plays a significant role in the sorptive stabilization of DOC.« less

Sorption of chlorophenols from aqueous solution by granular activated carbon, filter coal, pine and hardwood.

PubMed

Hossain, G S M; McLaughlan, R G

2012-09-01

Wood and coal, as low-cost sorbents, have been evaluated as an alternative to commercial granular activated carbon (GAC) for chlorophenol removal. Kinetic experiments indicated that filter coal had a significantly lower rate of uptake (approximately 10% of final uptake was achieved after three hours) than the other sorbents, owing to intra-particle diffusion limitations. The data fitted a pseudo-second-order model. Sorption capacity data showed that GAC had a high sorption capacity (294-467 mg g(-1)) compared with other sorbents (3.2-7.5 mg(g-1)). However, wood and coal had a greater sorption capacity per unit surface area than GAC. Sorption equilibrium data was best predicted using a Freundlich adsorption model. The sorption capacity for all sorbents was 2-chlorophenol < 4-chlorophenol < 2, 4-dichlorophenol, which correlates well with solute hydrophobicity, although the relative differences were much less for coal than the other sorbents. The results showed that pine, hardwood and filter coal can be used as sorbent materials for the removal of chlorophenol from water; however, kinetic considerations may limit the application of filter coal.

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin.

PubMed

Wilson, Lee D; Mohamed, Mohamed H; Berhaut, Christopher L

2011-08-29

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 10¹ m²/g), CDI-X copolymers (< 10¹ m²/g), and granular activated carbon (GAC ~10³ m²/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material.

Mechanism of and relation between the sorption and desorption of nonylphenol on black carbon-inclusive sediment.

PubMed

Liping, Lou; Guanghuan, Cheng; Jingyou, Deng; Mingyang, Sun; Huanyu, Chen; Qiang, Yang; Xinhua, Xu

2014-07-01

Correlation between the sorption and desorption of nonylphenol (NP) and binary linear regression were conducted to reveal the underlying mechanism of and relation between sorption domains and desorption sites in black carbon (BC)-amended sediment. The sorption and desorption data could be fitted well using dual-mode (R(2) = 0.971-0.996) and modified two-domain model (R(2) = 0.986-0.995), respectively, and there were good correlations between these two parts of parameters (R(2) = 0.884-0.939, P < 0.01). The NP percentage in desorbable fraction was almost equal to that of the partition fraction, suggesting the desorbed NP came from linear partition domain, whereas the resistant desorption NP was segregated in nonlinear adsorption sites, which were dominated by pores in BC-amended sediment. Our investigation refined theory about the relation between sorption domains and desorption sites in sediment and could be used to predict the release risk of NP using sorption data when BC is used for NP pollution control. Copyright © 2014 Elsevier Ltd. All rights reserved.

Sorption of Aromatic Compounds with Copolymer Sorbent Materials Containing β-Cyclodextrin

PubMed Central

Wilson, Lee D.; Mohamed, Mohamed H.; Berhaut, Christopher L.

2011-01-01

Urethane copolymer sorbent materials that incorporate β-cyclodextrin (CD) have been prepared and their sorption properties with chlorinated aromatic compounds (i.e., pentachlorophenol, 2,4-dichlorophenol and 2,4-dichlorophenoxy acetic acid) have been evaluated. The sorption properties of granular activated carbon (GAC) were similarly compared in aqueous solution at variable pH conditions. The sorbents displayed variable BET surface areas as follows: MDI-X copolymers (< 101 m2/g), CDI-X copolymers (< 101 m2/g), and granular activated carbon (GAC ~103 m2/g). The sorption capacities for the copolymers sorbents are listed in descending order, as follows: GAC > CDI-3 copolymer ≈ MDI-3 copolymer. The sorption capacity for the aromatic adsorbates with each sorbent are listed in descending order, as follows: 2,4-dichlorophenol > 2,4-dichlorophenoxy acetic acid > pentachlorophenol. In general, the differences in the sorption properties of the copolymer sorbents with the chlorinated organics were related to the following factors: (i) surface area of the sorbent; (ii) CD content and accessibility; and (iii) and the chemical nature of the sorbent material. PMID:28824156

Potential phosphorus eutrophication mitigation strategy: Biochar carbon composition, thermal stability and pH influence phosphorus sorption

Treesearch

L.W. Ngatia; Y.P. Hsieh; D. Nemours; R. Fu; R.W. Taylor

2017-01-01

Phosphorus (P) eutrophication is a major pollution problem globally, with unprecedented amount of P emanating from agricultural sources. But little is known about the optimization of soil-biochar P sorption capacity. The study objective was to determine how biochar feedstocks and pyrolysis conditions influences carbon (C) thermal stability, C composition and pH and in...

Ultraselective Carbon Molecular Sieve Membranes with Tailored Synergistic Sorption Selective Properties.

PubMed

Zhang, Chen; Koros, William J

2017-09-01

Membrane-based separations can reduce the energy consumption and the CO 2 footprint of large-scale fluid separations, which are traditionally practiced by energy-intensive thermally driven processes. Here, a new type of membrane structure based on nanoporous carbon is reported, which, according to this study, is best referred to as carbon/carbon mixed-matrix (CCMM) membranes. The CCMM membranes are formed by high-temperature (up to 900 °C) pyrolysis of polyimide precursor hollow-fiber membranes. Unprecedentedly high permselectivities are seen in CCMM membranes for CO 2 /CH 4 , N 2 /CH 4 , He/CH 4 , and H 2 /CH 4 separations. Analysis of permeation data suggests that the ultrahigh selectivities result from substantially increased sorption selectivities, which is hypothetically owing to the formation of ultraselective micropores that selectively exclude the bulkier CH 4 molecules. With tunable sorption selectivities, the CCMM membranes outperform flexible polymer membranes and traditional rigid molecular-sieve membranes. The capability to increase sorption selectivities is a powerful tool to leverage diffusion selectivities, and has opened the door to many challenging and economically important fluid separations that require ultrafine differentiation of closely sized molecules. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sorption of trivalent lanthanides and actinides onto montmorillonite: Macroscopic, thermodynamic and structural evidence for ternary hydroxo and carbonato surface complexes on multiple sorption sites.

PubMed

Fernandes, M Marques; Scheinost, A C; Baeyens, B

2016-08-01

The credibility of long-term safety assessments of radioactive waste repositories may be greatly enhanced by a molecular level understanding of the sorption processes onto individual minerals present in the near- and far-fields. In this study we couple macroscopic sorption experiments to surface complexation modelling and spectroscopic investigations, including extended X-ray absorption fine structure (EXAFS) and time-resolved laser fluorescence spectroscopies (TRLFS), to elucidate the uptake mechanism of trivalent lanthanides and actinides (Ln/An(III)) by montmorillonite in the absence and presence of dissolved carbonate. Based on the experimental sorption isotherms for the carbonate-free system, the previously developed 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model needed to be complemented with an additional surface complexation reaction onto weak sites. The fitting of sorption isotherms in the presence of carbonate required refinement of the previously published model by reducing the strong site capacity and by adding the formation of Ln/An(III)-carbonato complexes both on strong and weak sites. EXAFS spectra of selected Am samples and TRLFS spectra of selected Cm samples corroborate the model assumptions by showing the existence of different surface complexation sites and evidencing the formation of Ln/An(III) carbonate surface complexes. In the absence of carbonate and at low loadings, Ln/An(III) form strong inner-sphere complexes through binding to three Al(O,OH)6 octahedra, most likely by occupying vacant sites in the octahedral layers of montmorillonite, which are exposed on {010} and {110} edge faces. At higher loadings, Ln/An(III) binds to only one Al octahedron, forming a weaker, edge-sharing surface complex. In the presence of carbonate, we identified a ternary mono- or dicarbonato Ln/An(III) complex binding directly to one Al(O,OH)6 octahedron, revealing that type-A ternary complexes form with the one or two carbonate groups pointing away from the surface into the solution phase. Within the spectroscopically observable concentration range these complexes could only be identified on the weak sites, in line with the small strong site capacity suggested by the refined sorption model. When the solubility of carbonates was exceeded, formation of an Am carbonate hydroxide could be identified. The excellent agreement between the thermodynamic model parameters obtained by fitting the macroscopic data, and the spectroscopically identified mechanisms, demonstrates the mature state of the 2SPNE SC/CE model for predicting and quantifying the retention of Ln/An(III) elements by montmorillonite-rich clay rocks. Copyright © 2016 Elsevier Ltd. All rights reserved.

Carbon-Based Regenerable Sorbents for the Combined Carbon Dioxide and Ammonia Removal for the Primary Life Support System (PLSS)

NASA Technical Reports Server (NTRS)

Wojtowicz, Marek A.; Cosgrove, Joseph E.; Serio, Michael A.; Manthina, Venkata; Singh, Prabhakar; Chullen, Cinda

2014-01-01

Results are presented on the development of reversible sorbents for the combined carbon dioxide and trace-contaminant (TC) removal for use in Extravehicular Activities (EVAs). Since ammonia is the most important TC to be captured, data on TC sorption presented in this paper are limited to ammonia, with results relevant to other TCs to be reported at a later time. The currently available life support systems use separate units for carbon dioxide, trace contaminants, and moisture control, and the long-term objective is to replace the above three modules with a single one. Furthermore, the current TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal, which is non-regenerable, and the carbon-based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. The objective of this study was to demonstrate the feasibility of using carbon sorbents for the reversible, concurrent sorption of carbon dioxide and ammonia. Several carbon sorbents were fabricated and tested, and multiple adsorption/vacuum-regeneration cycles were demonstrated at room temperature, and also a carbon surface conditioning technique that enhances the combined carbon dioxide and ammonia sorption without impairing sorbent regeneration.

Activated Carbon-hydrogen based Continuous Sorption Cooling in Single Adsorbent Bed with LN2 Heat Sink

NASA Astrophysics Data System (ADS)

Koley, Susmita; Ghosh, Indranil

Quick and periodic inflow-outflow of adsorbate in an adsorbent column createsa differential temperature between the two ends of it, allowing for the generation of continuous sorption cooling in a single adsorbent tube. The concept has been proven experimentally and theoretically for near room temperature applications using activated carbon-nitrogen. The feasibility of generating continuous solid sorption cooling in a single adsorbent tube in the cryogenic domainhas been studied theoretically with a different adsorbent-adsorbate pair, namely, activated carbon-hydrogen. Precooling of gaseous hydrogen (before it enters the adsorbent column) and removal of the heat of adsorption has been achieved using liquid nitrogen. Theoretical estimation shows nearly 20 K temperature difference between the two ends under no load condition. Finally, parametric variations have been performed.

Copper modified carbon molecular sieves for selective oxygen removal

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor); Seshan, Panchalam K. (Inventor)

1992-01-01

Carbon molecular sieves modified by the incorporation of finely divided elemental copper useful for the selective sorption of oxygen at elevated temperatures. The carbon molecular sieves can be regenerated by reduction with hydrogen. The copper modified carbon molecular sieves are prepared by pyrolysis of a mixture of a copper-containing material and polyfunctional alcohol to form a sorbent precursor. The sorbent precursors are then heated and reduced to produce copper modified carbon molecular sieves. The copper modified carbon molecular sieves are useful for sorption of all concentrations of oxygen at temperatures up to about 200.degree. C. They are also useful for removal of trace amount of oxygen from gases at temperatures up to about 600.degree. C.

Effects of natural organic matter on PCB-activated carbon sorption kinetics: implications for sediment capping applications.

PubMed

Fairey, Julian L; Wahman, David G; Lowry, Gregory V

2010-01-01

In situ capping of polychlorinated biphenyl (PCB)-contaminated sediments with a layer of activated carbon has been proposed, but several questions remain regarding the long-term effectiveness of this remediation strategy. Here, we assess the degree to which kinetic limitations, size exclusion effects, and electrostatic repulsions impaired PCB sorption to activated carbon. Sorption of 11 PCB congeners with activated carbon was studied in fixed bed reactors with organic-free water (OFW) and Suwannee River natural organic matter (SR-NOM), made by reconstituting freeze-dried SR-NOM at a concentration of 10 mg L(-1) as carbon. In the OFW test, no PCBs were detected in the column effluent over the 390-d study, indicating that PCB-activated carbon equilibrium sorption capacities may be achieved before breakthrough even at the relatively high hydraulic loading rate (HLR) of 3.1 m h(-1). However, in the SR-NOM fixed-bed test, partial PCB breakthrough occurred over the entire 320-d test (HLRs of 3.1-, 1.5-, and 0.8 m h(-1)). Simulations from a modified pore and surface diffusion model indicated that external (film diffusion) mass transfer was the dominant rate-limiting step but that internal (pore diffusion) mass transfer limitations were also present. The external mass transfer limitation was likely caused by formation of PCB-NOM complexes that reduced PCB sorption through a combination of (i) increased film diffusion resistance; (ii) size exclusion effects; and (iii) electrostatic repulsive forces between the PCBs and the NOM-coated activated carbon. However, the seepage velocities in the SR-NOM fixed bed test were about 1000 times higher than would be expected in a sediment cap. Therefore, additional studies are needed to assess whether the mass transfer limitations described here would be likely to manifest themselves at the lower seepage velocities observed in practice.

SORPTION OF 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN FROM WATER BY SURFACE SOILS

EPA Science Inventory

The sorption of l4C-labeled 2,3,7,8-tetrachlorodibenzo- p-dioxin (TCDD) from water by two uncontaminated surface soils from the Times Beach, MO, area was evalu- ated by using batch shake testing. Sorption isotherm plots for the soil with the lower fraction organic carbon (f,) wer...

Laboratory simulation of meteoritic noble gases. III - Sorption of neon, argon, krypton, and xenon on carbon - Elemental fractionation

NASA Technical Reports Server (NTRS)

Wacker, John F.

1989-01-01

The sorption of Ne, Ar, Kr, and Xe was studied in carbon black, acridine carbon, and diamond in an attempt to understand the origin of trapped noble gases in meteorites. The results support a model in which gases are physically adsorbed on interior surfaces formed by a pore labyrinth within amorphous carbons. The data show that: (1) the adsorption/desorption times are controlled by choke points that restrict the movement of noble gas atoms within the pore labyrinth, and (2) the physical adsorption controls the temperature behavior and elemental fractionation patterns.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hur, Tae-Bong; Fazio, James; Romanov, Vyacheslav

Due to increasing atmospheric CO2 concentrations causing the global energy and environmental crises, geological sequestration of carbon dioxide is now being actively considered as an attractive option to mitigate greenhouse gas emissions. One of the important strategies is to use deep unminable coal seams, for those generally contain significant quantities of coal bed methane that can be recovered by CO2 injection through enhanced coal bed natural gas production, as a method to safely store CO2. It has been well known that the adsorbing CO2 molecules introduce structural deformation, such as distortion, shrinkage, or swelling, of the adsorbent of coal organicmore » matrix. The accurate investigations of CO2 sorption capacity as well as of adsorption behavior need to be performed under the conditions that coals deform. The U.S. Department of Energy-National Energy Technology Laboratory and Regional University Alliance are conducting carbon dioxide sorption isotherm experiments by using manometric analysis method for estimation of CO2 sorption capacity of various coal samples and are constructing a gravimetric apparatus which has a visual window cell. The gravimetric apparatus improves the accuracy of carbon dioxide sorption capacity and provides feasibility for the observation of structural deformation of coal sample while carbon dioxide molecules interact with coal organic matrix. The CO2 sorption isotherm measurements have been conducted for moist and dried samples of the Central Appalachian Basin (Russell County, VA) coal seam, received from the SECARB partnership, at the temperature of 55 C.« less

Sorption interactions of heavy metals with biochar in soil remediation studies

NASA Astrophysics Data System (ADS)

Fristak, Vladimir; Friesl-Hanl, Wolfgang; Wawra, Anna; Soja, Gerhard

2015-04-01

The search for new materials in soil remediation applications has led to new conversion technologies such as carbonization and pyrolysis. Biochar represents the pyrolytic product of different biomass input materials processed at 350-1000°C and anoxic conditions. The pyrolysis temperature and feedstock have a considerable influence on the quality of the charred product and also its main physico-chemical properties. Biochar as porous material with large specific surface and C-stability is utilized in various environmental and agricultural technologies. Carbon sequestration, increase of soil water-holding capacity and pH as well as sorption of different xenobiotics present only a fraction of the multitude of biochar application possibilities. Heavy metals as potential sources of ecotoxicological risks are characterized by their non-degradability and the potential transfer into the food chain. Carbonaceous materials have been used for a long time as sorbents for heavy metals and organic contaminants in soil and water technologies. The similarity of biochar with activated carbon predetermines this material as remediation tool which plays an important role in heavy metal immobilization and retention with a parallel reduction in the risk of ground water and food crop contamination. In all this processes the element-specific sorption behaviour of biochar creates new conditions for pollutant binding. Sorption interaction and separation of contaminants from soil solution or waste effluent can be affected by wide-ranging parameters. In detail, our study was based on batch-sorption comparisons of two biochars produced from wood chips and green waste residues. We observed that sorption efficiency of biochar for model bivalent heavy metals (Cd, Zn, Cu) can be influenced by equilibrium parameters such as pH, contact time, initial concentration of metal in reaction solutions, presence of surfactants and chemical modification by acid hydrolysis, esterification and methylation. The study of sorption mechanisms showed differences in the sorption of the targeted heavy metals in relation to the contribution of ion-exchange and precipitation processes. We confirmed the effectivity of physico-chemical artificial aging on sorption capacity of biochar in terms of changes in surface structure. Based on these results, the application potential of biochar as sorption material for stabilizing heavy metals in soils is discussed.

Linear and non-linear regression analysis for the sorption kinetics of methylene blue onto activated carbon.

PubMed

Kumar, K Vasanth

2006-10-11

Batch kinetic experiments were carried out for the sorption of methylene blue onto activated carbon. The experimental kinetics were fitted to the pseudo first-order and pseudo second-order kinetics by linear and a non-linear method. The five different types of Ho pseudo second-order expression have been discussed. A comparison of linear least-squares method and a trial and error non-linear method of estimating the pseudo second-order rate kinetic parameters were examined. The sorption process was found to follow a both pseudo first-order kinetic and pseudo second-order kinetic model. Present investigation showed that it is inappropriate to use a type 1 and type pseudo second-order expressions as proposed by Ho and Blanachard et al. respectively for predicting the kinetic rate constants and the initial sorption rate for the studied system. Three correct possible alternate linear expressions (type 2 to type 4) to better predict the initial sorption rate and kinetic rate constants for the studied system (methylene blue/activated carbon) was proposed. Linear method was found to check only the hypothesis instead of verifying the kinetic model. Non-linear regression method was found to be the more appropriate method to determine the rate kinetic parameters.

Sorption of agrochemical model compounds by sorbent materials containing beta-cyclodextrin.

PubMed

Wilson, Lee D; Mohamed, Mohamed H; Guo, Rui; Pratt, Dawn Y; Kwon, Jae Hyuck; Mahmud, Sarker T

2010-04-01

Polymeric sorbent materials that incorporate beta-cyclodextrin (CD) have been prepared and their sorption behavior toward two model agrochemical contaminant compounds, p-nitrophenol (PNP) and methyl chloride examined. The sorption of PNP was studied in aqueous solution using ultraviolet-visible (UV-Vis) spectroscopy, whereas the sorption of methyl chloride from the gas phase was studied using a Langmuir adsorption method. The sorption results for PNP in solution were compared between granular activated carbon (GAC), modified GAC, CD copolymers, and CD-based mesoporous silica hybrid materials. Nitrogen porosimetry at 77 K was used to estimate the surface area and pore structure properties of the sorbent materials. The sorbents displayed variable surface areas as follows: copolymers (36.2-157 m(2)/g), CD-silica materials (307-906 m(2)/g), surface modified GAC (657 m(2)/g), and granular activated carbon (approximately 10(3) m(2)/g). The sorption capacities for PNP and methyl chloride with the different sorbents are listed in descending order as follows: GAC > copolymers > surface modified GAC > CD-silica hybrid materials. In general, the differences in the sorption properties of the sorbents were related to the following: (i) surface area of the sorbent, (ii) CD content and accessibility, (iii) and the chemical nature of the sorbent material.

Solid phase extraction of uranium(VI) onto benzoylthiourea-anchored activated carbon.

PubMed

Zhao, Yongsheng; Liu, Chunxia; Feng, Miao; Chen, Zhen; Li, Shuqiong; Tian, Gan; Wang, Li; Huang, Jingbo; Li, Shoujian

2010-04-15

A new solid phase extractant selective for uranium(VI) based on benzoylthiourea anchored to activated carbon was developed via hydroxylation, amidation and reaction with benzoyl isothiocyanate in sequence. Fourier transform infrared spectroscopy and total element analysis proved that benzoylthiourea had been successfully grafted to the surface of the activated carbon, with a loading capacity of 1.2 mmol benzoylthiourea per gram of activated carbon. The parameters that affect the uranium(VI) sorption, such as contact time, solution pH, initial uranium(VI) concentration, adsorbent dose and temperature, have been investigated. Results have been analyzed by Langmuir and Freundlich isotherm; the former was more suitable to describe the sorption process. The maximum sorption capacity (82 mg/g) for uranium(VI) was obtained at experimental conditions. The rate constant for the uranium sorption by the as-synthesized extractant was 0.441 min(-1) from the first order rate equation. Thermodynamic parameters (DeltaH(0)=-46.2 kJ/mol; DeltaS(0)=-98.0 J/mol K; DeltaG(0)=-17.5 kJ/mol) showed the adsorption of an exothermic process and spontaneous nature, respectively. Additional studies indicated that the benzoylthiourea-anchored activated carbon (BT-AC) selectively sorbed uranyl ions in the presence of competing ions, Na(+), Co(2+), Sr(2+), Cs(+) and La(3+). 2009 Elsevier B.V. All rights reserved.

High-pressure sorption of nitrogen, carbon dioxide, and their mixtures on Argonne Premium Coals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Andreas Busch; Yves Gensterblum; Bernhard M. Krooss

2007-06-15

Gas sorption isotherms have been measured for carbon dioxide and nitrogen and their binary mixture (N{sub 2}/CO{sub 2} {approximately} 80/20) on three different moisture-equilibrated coals from the Argonne Premium Coal Sample Program by the U.S. Department of Energy, varying in rank from 0.25 to 1.68% vitrinite reflectance (VR{sub r}). The measurements were conducted at 55 C and at pressures up to 27 MPa for the pure gases and up to 10 MPa for the gas mixture. The effects of the large differences in equilibrium moisture contents (0.8 to 32.2%) on sorption capacity were estimated on the basis of the aqueousmore » solubility of CO{sub 2} and N{sub 2} at experimental conditions. Especially for the Beulah-Zap coal with an equilibrium moisture content of {approximately} 32%, the amount of dissolved CO{sub 2} contributes significantly to the overall storage capacity, whereas the amounts of N{sub 2} dissolved in the moisture water are low and can be neglected. Sorption measurements with nitrogen/carbon dioxide mixtures showed very low capacities for N{sub 2}. For Illinois coal, these excess sorption values were even slightly negative, probably due to small volumetric effects (changes in condensed phase volume). The evolution of the composition of the free gas phase in contact with the coal sample has been monitored continuously during each pressure step of the sorption tests. This composition changed strongly over time. Apparently, CO{sub 2} reaches sorption sites very quickly initially and is subsequently partly replaced by N{sub 2} molecules until concentration equilibration is reached. 18 refs., 10 figs., 2 tabs.« less

Gas sorption in poly-(2,6-dimethyl-1,4-phenylene)oxide containing nanoporous crystalline phases

NASA Astrophysics Data System (ADS)

Galizia, M.; Daniel, C.; Fasano, G.; Guerra, G.; Mensitieri, G.

2012-07-01

In this contribution is presented an analysis of mass transport properties of low molecular weight compounds in amorphous PPO and in semi-crystalline PPO obtained by treating with benzene and carbon tetrachloride the amorphous sample. It is found that semi-crystalline samples are endowed with larger gas sorption capacity and diffusivity as compared to the amorphous ones: this behaviour has been attributed to the nanoporous nature of the crystalline phases induced by treatment with solvents. In particular, sorption experiments, carried out at 30°C with methane, carbon dioxide, propane and propylene, have shown that both semi-crystalline PPOs display rather interesting features which make them suitable for use as membrane materials in gas separation processes, in view of the relatively high values of solubility and diffusivity. Moreover, these peculiar sorption and mass transport properties have been found to be virtually unaffected by thermal ageing: in fact, sorption experiments conducted on amorphous and semi-crystalline PPO after treatment at 65°C for three months showed that sorption properties of aged samples are the same as for the untreated samples. This is an important feature to assure the stability of performances in membrane applications.

Copper crystallite in carbon molecular sieves for selective oxygen removal

NASA Technical Reports Server (NTRS)

Sharma, Pramod K. (Inventor); Seshan, Panchalam K. (Inventor)

1993-01-01

Carbon molecular sieves modified by the incorporation of finely divided elemental copper useful for the selective sorption of oxygen at elevated temperatures. The carbon molecular sieves can be regenerated by reduction with hydrogen. The copper modified carbon molecular sieves are prepared by pyrolysis of a mixture of a copper-containing material and polyfurfuryl alcohol to form a sorbent precursor. The sorbent precursors are then heated and reduced to produce copper modified carbon molecular sieves. The copper modified carbon molecular sieves are useful for sorption of all concentrations of oxygen at temperatures up to about 200.degree. C. They are also useful for removal of trace amount of oxygen from gases at temperatures up to about 600.degree. C.

Sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on the surface of porous graphitized carbon

NASA Astrophysics Data System (ADS)

Savchenkova, A. S.; Buryak, A. K.; Kurbatova, S. V.

2015-09-01

The sorption of 4-carboxyquinoline derivatives from aqueous acetonitrile solutions on porous graphitized carbon was studied. The effect of the structure of analyte molecules and the eluent composition on the characteristics of retention under the conditions of RP HPLC was analyzed. The effect of pH of the eluent on the shift of equilibrium in aqueous acetonitrile solutions was investigated.

Using Weighted Least Squares Regression for Obtaining Langmuir Sorption Constants

USDA-ARS?s Scientific Manuscript database

One of the most commonly used models for describing phosphorus (P) sorption to soils is the Langmuir model. To obtain model parameters, the Langmuir model is fit to measured sorption data using least squares regression. Least squares regression is based on several assumptions including normally dist...

Sensitivity of Deep Soil Organic Carbon Age to Sorption, Transport and Microbial Interactions - Insights from a Calibrated Process Model

NASA Astrophysics Data System (ADS)

Ahrens, B.; Schrumpf, M.; Reichstein, M.

2013-12-01

Subsoil soil organic carbon (SOC) is characterized by conventional radiocarbon ages on the order of centuries to millennia. Most vertically explicit SOC turnover models represent this persistence of deep SOC by one pool that has millennial turnover times. This approach lumps different stabilizing mechanisms such as chemical recalcitrance, sorptive stabilization and energy limitation into a single rate constant. As an alternative, we present a continuous, vertically explicit SOC decomposition model that allows for stabilization via sorption and microbial interactions (COMISSION model). We compare the COMISSION model with the SOC profile of a Haplic Podzol under a Norway spruce forest. In the COMISSION model two pools receive aboveground litter input and vertically distributed root litter input. The readily leachable and soluble fraction of litter input enters a dissolved organic carbon pool (DOC), while the rest enters the residue pool which represents polymeric, non-soluble SOC. The residue pool is depolymerized with extracellular enzymes produced by a microbial pool to enter the DOC pool which represents SOC potentially available for assimilation by microbes. The adsorption/desorption of DOC from/to mineral surfaces controls the availability of carbon in the DOC pool for assimilatory uptake by microbes. The sorption of DOC is modeled with dynamic Langmuir equations. The desorbed part of the DOC pool not only constitutes the substrate for the microbial pool, but is also transported via advection. Interactions of microbes with the residue and DOC pool are modeled with Michaelis-Menten kinetics - this not only allows representing ';priming', but also the retardation of decomposition via energy limitation in the deep soil where substrate is scarce. Further, soil organic matter is recycled within the soil profile through microbial processing - dead microbes either enter the DOC or the residue pool, and thereby also contribute to longer residence times with soil depth. First results of a calibration against SOC, SO14C, MOC and MO14C profiles (mineral associated organic carbon, density fraction >1.6 g cm-3) of a Haplic Podzol of the Waldstein site (Germany) show that we can use the maximum sorption capacity (qmax) estimated from batch sorption experiments to parameterize the dynamic Langmuir sorption equation. qmax could potentially be extrapolated to other soil profiles based on relations to iron and aluminum oxide contents. Although we are able to capture the secondary maximum of SOC contents in the Bh horizon with qmax from batch sorption experiments, our results indicate that the adsorption and desorption rates retrieved from batch sorption experiments are too fast to explain the low Δ14C values of the MOC. This could point to other processes apart from DOC sorption that trigger stabilization by organo-mineral associations with a stronger apparent irreversibility (e.g. inclusion in small pores). Alternatively, the conditions of batch sorption experiments (constant shaking in centrifuge tubes) might not be representative for in situ sorption conditions. Overall, we show how effective decomposition rates and 14C ages readily emerge from a combination of known stabilizing and destabilizing mechanisms and we discuss how to identify these processes with a model-data fusion framework.

Sorption of organic carbon compounds to the fine fraction of surface and Subsurface Soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jagadamma, Sindhu; Mayes, Melanie; Zinn, Yuri

2014-01-01

Dissolved organic carbon (DOC) transported from the soil surface is stabilized in deeper soil profiles by physicochemical sorption processes. However, it is unclear how different forms of organic carbon (OC) compounds common in soil organic matter interact with soil minerals in the surface (A) and subsurface (B) horizons. We added four compounds (glucose, starch, cinnamic acid and stearic acid) to the silt- and clay-sized fraction (fine fraction) of A and B horizons of eight soils from varying climates (3 temperate, 3 tropical, 1 arctic and 1 sub-arctic). Equilibriumbatch experiments were conducted using 0 to 100 mg C L 1 ofmore » 14C-labeled compounds for 8 h. Sorption parameters (maximum sorption capacity, Qmax and binding coefficient, k) calculated by fitting sorption data to the Langmuir equation showed that Qmax of A and B horizons was very similar for all compounds. Both Qmax and k values were related to sorbate properties, with Qmax being lowest for glucose (20 500 mg kg 1), highest for stearic acid (20,000 200,000 mg kg 1), and intermediate for both cinnamic acid (200 4000 mg kg 1) and starch (400 6000 mg kg 1). Simple linear regression analysis revealed that physicochemical properties of the sorbents influenced the Qmax of cinnamic acid and stearic acid, but not glucose and starch. The sorbent properties did not show predictive ability for binding coefficient k. By using the fine fraction as sorbent, we found that the mineral fractions of A horizons are equally reactive as the B horizons irrespective of soil organic carbon content.« less

Pyrochars and hydrochars differently alter the sorption of the herbicide isoproturon in an agricultural soil.

PubMed

Eibisch, Nina; Schroll, Reiner; Fuß, Roland; Mikutta, Robert; Helfrich, Mirjam; Flessa, Heinz

2015-01-01

Carbonaceous material from pyrolysis (pyrochars) and hydrothermal carbonization (hydrochars) are applied to soil to improve soil fertility and carbon sequestration. As a positive side effect, the mobility of pesticides and the risk of groundwater contamination can be minimized. However, the impact of various raw materials on the sorption capacity of different pyrochars and hydrochars is poorly understood. Thus, sorption experiments were performed with (14)C-labeled isoproturon (IPU, 0.75 kg ha(-1)) in a loamy sand soil amended with either pyrochar or hydrochar (0.5% and 5% dry weight, respectively). Carbonaceous materials were produced from three different raw materials: corn digestate, miscanthus, woodchips of willow and poplar. After 72 h of incubation, a sequential extraction procedure was conducted to quantify in situ IPU bioavailability, total amount of extractable IPU, and non-extractable pesticide residues (NER). Added char amount, carbonization type, and raw materials had statistically significant effects on the sorption of IPU. The amount of in situ available IPU was reduced by a factor of 10-2283 in treatments with pyrochar and by a factor of 3-13 in hydrochar treatments. The surface area of the charred material was the most predictive variable of IPU sorption to char amended soil. Some physical and chemical char properties tend to correlate with pore water-, methanol- or non-extractable IPU amounts. Due to a low micro-porosity and ash content, high water extractable carbon contents and O-functional groups of hydrochars, the proportion of NER in hydrochar amended soils was considerably lower than in soil amended with pyrochars. Copyright © 2014 Elsevier Ltd. All rights reserved.

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

USGS Publications Warehouse

Barber, L.B.; Thurman, E.M.; Runnells, D.R.; ,

1992-01-01

The effect of particle size, mineralogy and sediment organic carbon (SOC) on solution of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5-25% of the bulk sediment. Although SOC content of the bulk sediment is < 0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5-25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

Behavior and Fate of PFOA and PFOS in Sandy Aquifer ...

EPA Pesticide Factsheets

Microcosms were constructed with sediment from beneath a landfill that received waste containing PFOA (perfluorooctanoic acid) and PFOS (perfluorooctane sulfonate). The microcosms were amended with PFOA and PFOS, and sampled after 91, 210, 343, 463, 574, and 740 days of incubation. After 740 days, selected microcosms were extracted to determine the mass of PFOA and PFOS remaining. There was no evidence for degradation of PFOA or PFOS. Over time, the aqueous concentrations of PFOA and PFOS increased in the microcosms, indicating that PFOA and PFOS that had originally sorbed to the sediment was desorbing. At the beginning of the experiment, the adsorption coefficient, Kd, averaged 0.27 L/kg for PFOA and 1.2 L/kg for PFOS. After 740 days of incubation, sorption of PFOA was not detectable and the Kd of PFOS was undetectable in two microcosms and was 0.08 L/kg in a third microcosm. During incubation, the pH of the pore water in the microcosms increased from pH 7.2 to pH ranging from 8.1 to 8.8 and the zeta potential of the sediment decreased with increasing pH. These observations suggest sorption of PFOA and PFOS was controlled by electrostatic sorption on ferric oxide minerals, and not by sorption to organic carbon. These observations suggest sorption of PFOA and PFOS was controlled by electrostatic sorption on ferric oxide minerals, and not by sorption to organic carbon.

Effect of water saturation in soil organic matter on the partition of organic compounds

USGS Publications Warehouse

Rutherford, D.W.; Chlou, G.T.

1992-01-01

The sorption of benzene, trichloroethylene, and carbon tetrachloride at room temperature from water solution and from vapor on two high-organic-content soils (peat and muck) was determined in order to evaluate the effect of water saturation on the solute partition in soil organic matter (SOM). The uptake of water vapor was similarly determined to define the amounts of water in the saturated soil samples. In such high-organic-content soils the organic vapor sorption and the respective solute sorption from water exhibit linear isotherms over a wide range of relative concentrations. This observation, along with the low BET surface areas of the samples, suggests that partition in the SOM of the samples is the dominant process in the uptake of these liquids. A comparison of the sorption from water solution and from vapor phase shows that water saturation reduces the sorption (partition) efficiency of SOM by ?? 42%; the saturated water content is ??38% by weight of dry SOM. This reduction is relatively small when compared with the almost complete suppression by water of organic compound adsorption on soil minerals. While the effect of water saturation on solute uptake by SOM is much expected in terms of solute partition in SOM, the influence of water on the solubility behavior of polar SOM can be explained only qualitatively by regular solution theory. The results suggest that the major effect of water in a drying-wetting cycle on the organic compound uptake by normal low-organic-content soils (and the associated compound's activity) is the suppression of adsorption by minerals rather than the mitigation of the partition effect in SOM.

Effects of soil attributes and straw accumulation on the sorption of hexazinone and tebuthiuron in tropical soils cultivated with sugarcane.

PubMed

Pereira-Junior, Ernani V; Giori, Fabrício G; Nascimento, Altina L; Tornisielo, Valdemar L; Regitano, Jussara B

2015-01-01

Brazil is the largest sugarcane producer in the world in which hexazinone (3-cyclohexyl-6-dimethylamino-1-methyl-1,3,5-triazine-2,4-dione) and tebuthiuron (1-(5-tert-butyl-1,3,4-thiadiazol-2-yl)-1,3-dimethylurea) are heavily used. Sugarcane harvesting is changing from the manual system with previous straw burning to the mechanized system without straw burning. The lack of burning results in soil organic carbon accumulation mainly in clayey soils, which should affect herbicides availability and fate. Therefore, we evaluated sorption of these herbicides in soil samples with and without straw burning. Both herbicides presented low apparent sorption coefficients (mean K(d,app)= 0.6 and 2.4 L kg(-1) for hexazinone and tebuthiuron, respectively), suggesting that they may leach to groundwater. Moreover, their sorption correlated primarily with soil organic carbon (SOC), but iron oxide contents extracted with ammonium oxalate (Fe2O3(AOX)) also affected it (K(d,app) = -0.228 + 0.0397 SOC + 0.117 Fe2O3(AOX) for hexazinone and K(d,app) = -1.407 + 0.201 SOC + 0.348 Fe2O3(AOX) for tebuthiuron). Soil organic carbon accumulation due to straw maintenance in the field positively affected sorption of both herbicides, but its effects were not enough to classify them as "non-leachers."

Meta-analysis of pesticide sorption in subsoils

NASA Astrophysics Data System (ADS)

Jarvis, Nicholas

2017-04-01

It has been known for several decades that sorption koc values tend to be larger in soils that are low in organic carbon (i.e. subsoils). Nevertheless, in a regulatory context, the models used to assess leaching of pesticides to groundwater still rely on a constant koc value, which is usually measured on topsoil samples. This is mainly because the general applicability of any improved model approach that is also simple enough to use for regulatory purposes has not been demonstrated. The objective of this study was therefore first to summarize and generalize available literature data in order to assess the magnitude of any systematic increase of koc values in subsoil and to test an alternative model of subsoil sorption that could be useful in pesticide risk assessment and management. To this end, a database containing the results of batch sorption experiments for pesticides was compiled from published studies in the literature, which placed at least as much emphasis on measurements in subsoil horizons as in topsoil. The database includes 967 data entries from 46 studies and for 34 different active substances (15 non-ionic compounds, 13 weak acids, 6 weak bases). In order to minimize pH effects on sorption, data for weak acids and bases were only included if the soil pH was more than two units larger than the compound pKa. A simple empirical model, whereby the sorption constant is given as a power law function of the soil organic carbon content, gave good fits to most data sets. Overall, the apparent koc value, koc(app), for non-ionic compounds and weak bases roughly doubled as the soil organic carbon content decreased by a factor of ten. The typical increase in koc(app) was even larger for weak acids: on average koc(app) increased by a factor of six as soil organic carbon content decreased by a factor of ten. These results suggest the koc concept currently used in leaching models should be replaced by an alternative approach that gives a more realistic representation of pesticide sorption in subsoil. The model tested in this study appears to be widely applicable and simple enough to parameterize for risk assessment purposes. However, more data on subsoil sorption should first be included in the analysis to enable reliable estimation of worst-case percentile values of the power law exponent in the model.

Study on the sorption behaviour of estrone on marine sediments.

PubMed

Zhang, Jing; Yang, Gui-Peng; Li, Quan; Cao, Xiaoyan; Liu, Guangxing

2013-11-15

The sorption behaviour of estrone (E1) on marine sediments treated by different methods was systematically investigated. About 22 h was required for sorption equilibrium of E1. Sorption isotherms of E1 were well fitted with Freundlich model. The sorption behaviour of E1 on HCl-treatment and H2O-treatment sediments related significantly with the sediment organic carbon contents. Additionally, clay minerals and surface areas of sediments played dominant roles in the sorption of E1 on H2O2-treatment sediments. Some external factors which could affect sorption behaviour of E1 were also investigated. Our results showed that the sorption capacity of E1 on the sediments increased with the increasing concentrations of cationic surfactant cetyltrimethylammonium bromide (CTAB), nonionic surfactant polyoxyethylene (80) sorbitan esters (Tween 80) and salinity of seawater. In contrast, the sorption capacity of E1 decreased with the increasing concentration of anionic surfactant sodium dodecylbenzene sulfonate (SDBS), pH value and temperature of seawater. Copyright © 2013 Elsevier Ltd. All rights reserved.

Effect of exchangeable cation concentration on sorption and desorption of dissolved organic carbon in saline soils.

PubMed

Setia, Raj; Rengasamy, Pichu; Marschner, Petra

2013-11-01

Sorption is a very important factor in stabilization of dissolved organic carbon (DOC) in soils and thus C sequestration. Saline soils have significant potential for C sequestration but little is known about the effect of type and concentration of cations on sorption and release of DOC in salt-affected soils. To close this knowledge gap, three batch sorption and desorption experiments were conducted using soils treated with solutions either low or high in salinity. In Experiment 1, salinity was developed with either NaCl or CaCl2 to obtain an electrical conductivity (EC) in a 1:5 soil: water extract (EC1:5) of 2 and 4 dS m(-1). In Experiments 2 and 3, NaCl and CaCl2 were added in various proportions (between 25 and 100%) to obtain an EC1:5 of 0.5 and 4 dS m(-1), respectively. At EC1:5 of 4 dS m(-1), the sorption of DOC (derived from wheat straw) was high even at a low proportion of added Ca(2+) and did not change with proportion of Ca added, but at EC1:5 of 0.5 dS m(-1) increasing proportion of Ca(2+) added increased DOC sorption. This can be explained by the differences in exchangeable Ca(2+) at the two salinity levels. At EC1:5 of 4 dS m(-1), the exchangeable Ca(2+) concentration did not increase beyond a proportion of 25% Ca(2+), whereas it increased with increasing Ca(2+) proportion in the treatments at EC1:5 of 0.5 dS m(-1). The DOC sorption was lowest with a proportion of 100% as Na(+). When Ca(2+) was added, DOC sorption was highest, but least was desorbed (with deionised water), thus sorption and desorption of added DOC were inversely related. The results of this study suggest that DOC sorption in salt-affected soils is mainly controlled by the levels of exchangeable Ca(2+) irrespective of the Ca(2+) concentration in the soil solution which has implications on carbon stabilization in salt-affected soils. Copyright © 2013 Elsevier B.V. All rights reserved.

Sorption, desorption, and speciation of Cd, Ni, and Fe by four calcareous soils as affected by pH.

PubMed

Tahervand, Samaneh; Jalali, Mohsen

2016-06-01

The sorption, desorption, and speciation of cadmium (Cd), nickel (Ni), and iron (Fe) in four calcareous soils were investigated at the pH range of 2-9. The results indicated that sorption of Fe by four soils was higher than 80 % at pH 2, while in the case of Cd and Ni was less than 30 %. The most common sequence of metal sorption at pH 2-9 for four soils was in the order of Fe ≫ Ni > Cd. Cadmium and Ni sorption as a function of pH showed the predictable trend of increasing metal sorption with increase in equilibrium pH, while the Fe sorption trend was different and characterized by three phases. With regard to the order of Cd, Ni, and Fe sorption on soils, Cd and Ni showed high affinity for organic matter (OM), whereas Fe had high tendency for calcium carbonate (CaCO3). Results of metal desorption using 0.01 M NaCl demonstrated that metal sorption on soils containing high amounts of CaCO3 was less reversible in comparison to soils containing high OM. In general, Cd and Ni desorption curves were characterized by three phases; (1) the greatest desorption at pH 2, (2) the low desorption at pH 3-7, and (3) the least desorption at pH > 7. The MINTEQ speciation solubility program showed that the percentage of free metals declined markedly with increase of pH, while the percentage of carbonate and hydroxyl species increased. Furthermore, MINTEQ predicted that saturation index (SI) of metals increased with increasing pH.

Experimental studies and physically substantiated model of carbon dioxide emission from the exposed cultural layer of Velikii Novgorod

NASA Astrophysics Data System (ADS)

Smagin, A. V.; Dolgikh, A. V.; Karelin, D. V.

2016-04-01

The results of quantitative assessment and modeling of carbon dioxide emission from urban pedolithosediments (cultural layer) in the central part of Velikii Novgorod are discussed. At the first stages after the exposure of the cultural layer to the surface in archaeological excavations, very high CO2 emission values reaching 10-15 g C/(m2 h) have been determined. These values exceed the normal equilibrium emission from the soil surface by two orders of magnitude. However, they should not be interpreted as indications of the high biological activity of the buried urban sediments. A model based on physical processes shows that the measured emission values can be reliably explained by degassing of the soil water and desorption of gases from the urban sediments. This model suggests the diffusion mechanism of the transfer of carbon dioxide from the cultural layer into the atmosphere; in addition, it includes the equations to describe nonequilibrium interphase interactions (sorption-desorption and dissolution-degassing of CO2) with the first-order kinetics. With the use of statistically reliable data on physical parameters—the effective diffusion coefficient as dependent on the aeration porosity, the effective solubility, the Henry constant for the CO2 sorption, and the kinetic constants of the CO2 desorption and degassing of the soil solution—this model reproduces the experimental data on the dynamics of CO2 emission from the surface of the exposed cultural layer obtained by the static chamber method.

Carbon-coated Li3 N nanofibers for advanced hydrogen storage.

PubMed

Xia, Guanglin; Li, Dan; Chen, Xiaowei; Tan, Yingbin; Tang, Ziwei; Guo, Zaiping; Liu, Huakun; Liu, Zongwen; Yu, Xuebin

2013-11-20

3D porous carbon-coated Li3 N nanofibers are successfully fabricated via the electrospinning technique. The as-prepared nanofibers exhibit a highly improved hydrogen-sorption performance in terms of both thermodynamics and kinetics. More interestingly, a stable regeneration can be achieved due to the unique structure of the nanofibers, over 10 cycles of H2 sorption at a temperature as low as 250 °C. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sorption/Desorption and Transport of Trichloroethene in Freshly-amended, Synthetically- aged, and Field-contaminated Aquifer Material

NASA Astrophysics Data System (ADS)

Johnson, G. R.; Norris, D. K.; Brusseau, M. L.

2008-12-01

This study investigates the effect of long-term contaminant aging on the sorption/desorption and transport of trichloroethene in a low organic-carbon content aquifer material collected from the source zone of a chlorinated-solvent contaminated federal Superfund site in Arizona. This was accomplished by comparing elution behavior for field-contaminated, synthetically-aged (contact times of approximately four years), and freshly-amended aquifer material. Elution of trichloroethene exhibited extensive low-concentration tailing, despite minimal retention of trichloroethene by the aquifer material. The observed nonideal behavior indicates significant mass-transfer constraints influenced trichloroethene transport in this aquifer material. The elution behavior of trichloroethene for the field-contaminated and aged treatments was essentially identical to that observed for the fresh treatments. In addition, the results of three independent mass- balance analyses, total mass eluted, solvent-extraction analysis of residual sorbed mass, and flow- interruption rebound, showed equivalent recoveries for the aged and fresh treatments. These results indicate that long-term contaminant aging did not significantly influence the transport and fate behavior of trichloroethene in this low organic-carbon aquifer material. The observed nonideal behavior of trichloroethene (i.e., nonlinear sorption and significantly rate-limited sorption/desorption) suggests physically condensed carbonaceous material, comprising 61% of this media's organic-carbon content, mediates the transport and fate behavior of trichloroethene in this low organic-carbon content aquifer material.

Green Synthesis of Nanosilica from Coal Fly Ash and Its Stabilizing Effect on CaO Sorbents for CO2 Capture.

PubMed

Yan, Feng; Jiang, Jianguo; Li, Kaimin; Liu, Nuo; Chen, Xuejing; Gao, Yuchen; Tian, Sicong

2017-07-05

High-temperature sorption of CO 2 via calcium looping has wide applications in postcombustion carbon capture, sorption-enhanced hydrogen production, and inherent energy storage. However, fast deactivations of CaO sorbents and low CO 2 uptake in the fast carbonation stage are major drawbacks of this technology. For the first time, we developed a green approach through the reuse of nanosilica derived from coal fly ash (CFA) to enhance both the cyclic CO 2 uptakes and the sorption kinetics of CaO sorbents. The as-synthesized nanosilica-supported CaO sorbent showed superior cyclic stability even under realistic carbonation/calcination conditions, and maintained a final CO 2 uptake of 0.20 g(CO 2 ) g(sorbent) -1 within short carbonation time, markedly increased by 155% over conventional CaO sorbent. Significantly, it also exhibited very fast sorption rate and could achieve almost 90% of the total CO 2 uptake within ∼20 s after the second cycle, which is critical for practical applications. These positive effects were attributed to the formation of larnite (Ca 2 SiO 4 ) and the physical nanostructure of silica, which could yield and keep abundant reactive small pores directly exposed to CO 2 throughout multiple cycles. The proposed strategy, integrating the on-site recycling of CFA, appears to be promising for CO 2 abatement from coal-fired power plants.

Analytical method for dissolved-organic carbon fractionation

USGS Publications Warehouse

Leenheer, Jerry A.; Huffman, Edward W. D.

1979-01-01

A standard procedure for analytical-scale dissolved organic carbon fractionation is presented, whereby dissolved organic carbon in water is first fractionated by a nonionic macroreticular resin into acid, base, and neutral hydrophobic organic solute fractions, and next fractionated by ion-exchange resins into acid, base, and neutral hydrophilic solute fractions. The hydrophobic solutes are defined as those sorbed on a nonionic, acrylic-ester macroreticular resin and are differentiated into acid, base, and nautral fractions by sorption/desorption controlled by pH adjustment. The hydrophilic bases are next sorbed on strong-acid ion-exchange resin, followed by sorption of hydrophilic acids on a strong-base ion-exchange resin. Hydrophilic neutrals are not sorbed and remain dissolved in the deionized water at the end of the fractionation procedure. The complete fractionation can be performed on a 200-milliliter filtered water sample, whose dissolved organic carbon content is 5-25 mg/L and whose specific conductance is less than 2,000 μmhos/cm at 25°C. The applications of dissolved organic carbon fractionation analysis range from field studies of changes of organic solute composition with synthetic fossil fuel production, to fundamental studies of the nature of sorption processes.

Positron Spectroscopy of Nanodiamonds after Hydrogen Sorption

PubMed Central

Laptev, Roman; Abzaev, Yuri; Lider, Andrey; Ivashutenko, Alexander

2018-01-01

The structure and defects of nanodiamonds influence the hydrogen sorption capacity. Positronium can be used as a sensor for detecting places with the most efficient capture of hydrogen atoms. Hydrogenation of carbon materials was performed from gas atmosphere. The concentration of hydrogen absorbed by the sample depends on the temperature and pressure. The concentration 1.2 wt % is achieved at the temperature of 243 K and the pressure of 0.6 MPa. The hydrogen saturation of nanodiamonds changes the positron lifetime. Increase of sorption cycle numbers effects the positron lifetime, as well as the parameters of the Doppler broadening of annihilation line. The electron-positron annihilation being a sensitive method, it allows detecting the electron density fluctuation of the carbon material after hydrogen saturation. PMID:29324712

The effects of organic matter-mineral interactions and organic matter chemistry on diuron sorption across a diverse range of soils.

PubMed

Smernik, Ronald J; Kookana, Rai S

2015-01-01

Sorption of non-ionic organic compounds to soil is usually expressed as the carbon-normalized partition coefficient (KOC), because it is assumed that the main factor that influences the amount sorbed is the organic carbon content of the soil. However, KOC can vary by a factor of at least ten across a range of soils. We investigated two potential causes of variation in diuron KOC - organic matter-mineral interactions and organic matter chemistry - for a diverse set of 34 soils from Sri Lanka, representing a wide range of soil types. Treatment with hydrofluoric acid (HF-treatment) was used to concentrate soil organic matter. HF-treatment increased KOC for the majority of soils (average factor 2.4). We attribute this increase to the blocking of organic matter sorption sites in the whole soils by minerals. There was no significant correlation between KOC for the whole soils and KOC for the HF-treated soils, indicating that the importance of organic matter-mineral interactions varied greatly amongst these soils. There was as much variation in KOC across the HF-treated soils as there was across the whole soils, indicating that the nature of soil organic matter is also an important contributor to KOC variability. Organic matter chemistry, determined by solid-state (13)C nuclear magnetic resonance (NMR) spectroscopy, was correlated with KOC for the HF-treated soils. In particular, KOC increased with the aromatic C content (R=0.64, p=1×10(-6)), and decreased with O-alkyl C (R=-0.32, p=0.03) and alkyl C (R=-0.41, p=0.004) content. Copyright © 2014 Elsevier Ltd. All rights reserved.

Application of carbon foam for heavy metal removal from industrial plating wastewater and toxicity evaluation of the adsorbent.

PubMed

Lee, Chang-Gu; Song, Mi-Kyung; Ryu, Jae-Chun; Park, Chanhyuk; Choi, Jae-Woo; Lee, Sang-Hyup

2016-06-01

Electroplating wastewater contains various types of toxic substances, such as heavy metals, solvents, and cleaning agents. Carbon foam was used as an adsorbent for the removal of heavy metals from real industrial plating wastewater. Its sorption capacity was compared with those of a commercial ion-exchange resin (BC258) and a heavy metal adsorbent (CupriSorb™) in a batch system. The experimental carbon foam has a considerably higher sorption capacity for Cr and Cu than commercial adsorbents for acid/alkali wastewater and cyanide wastewater. Additionally, cytotoxicity test showed that the newly developed adsorbent has low cytotoxic effects on three kinds of human cells. In a pilot plant, the carbon foam had higher sorption capacity for Cr (73.64 g kg(-1)) than for Cu (14.86 g kg(-1)) and Ni (7.74 g kg(-1)) during 350 h of operation time. Oxidation pretreatments using UV/hydrogen peroxide enhance heavy metal removal from plating wastewater containing cyanide compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

Insights into the attenuated sorption of organic compounds on black carbon aged in soil.

PubMed

Luo, Lei; Lv, Jitao; Chen, Zien; Huang, Rixiang; Zhang, Shuzhen

2017-12-01

Sorption of organic compounds on fresh black carbons (BCs) can be greatly attenuated in soil over time. We examined herein the changes in surface properties of maize straw-derived BCs (biochars) after aged in a black soil and their effects on the sorptive behaviors of naphthalene, phenanthrene and 1,3-dinitrobenzene. Dissolved fulvic and humic acids extracted from the soil were used to explore the role of dissolved organic carbon (DOC) in the aging of biochars. Chromatography analysis indicated that DOC molecules with relatively large molecular weight were preferentially adsorbed on the biochars during the aging processes. DOC sorption led to blockage of the biochar's micropores according to N 2 and CO 2 adsorption analyses. Surface chemistry of the biochars was also substantially modified, with more O-rich functional groups on the aged biochars compared to the original biochars, as evidenced by Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS) analyses. The changes in both the physical and chemical surface properties of biochars by DOC led to significant attenuation of the sorption capacity and nonlinearity of the nonionic organic compounds on the aged biochars. Among the tested organic compounds, phenanthrene was the most attenuated in its sorption by the aging treatments, possibly because of its relatively large molecular size and hydrophobicity. The information can help gain a mechanistic understanding of interactions between BCs and organic compounds in soil environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Variability in goethite surface site density: evidence from proton and carbonate sorption.

PubMed

Villalobos, Mario; Trotz, Maya A; Leckie, James O

2003-12-15

Goethite is a representative iron oxide in natural environments due to its abundance and thermodynamic stability and may be responsible for many surface-mediated processes, including ion retention and mobility in aqueous settings. A large variability in morphologies and specific surface areas of goethite crystals exists but little work has been done to compare surface reactivity between them. The present work offers experimental evidence for the existence of an inverse relationship between sorption capacity for protons and carbonate ions and specific surface area of goethite for three synthetic goethite preparations spanning surface area differences by a factor of 2. An explanation for this was found by assuming a variable reactive site density between preparations in direct relationship to their sorption capacity based on congruency of carbonate sorption computed on a per-site basis. Previous evidence of maximum sorption capacities supports this explanation, and site density ratios between the goethites studied here were obtained. Triple layer surface complexation modeling was successful in describing adsorption data for all goethite preparations using equal stoichiometries. A new formulation of standard state for activities of surface species based on a 1.0 mole fraction of sites on the solid allowed transformation of the conventional molar concentration-based affinity constants to values based on site occupancy. In this fashion, by applying the appropriate site density ratios, a single set of affinity constant values was found that described accurately the adsorption data for all preparations.

Influence of competing inorganic cations on the ion exchange equilibrium of the monovalent organic cation metoprolol on natural sediment.

PubMed

Niedbala, Anne; Schaffer, Mario; Licha, Tobias; Nödler, Karsten; Börnick, Hilmar; Ruppert, Hans; Worch, Eckhard

2013-02-01

The aim of this study was to systematically investigate the influence of the mono- and divalent inorganic ions Na(+) and Ca(2+) on the sorption behavior of the monovalent organic cation metoprolol on a natural sandy sediment at pH=7. Isotherms for the beta-blocker metoprolol were obtained by sediment-water batch tests over a wide concentration range (1-100000 μg L(-1)). Concentrations of the competing inorganic ions were varied within freshwater relevant ranges. Data fitted well with the Freundlich sorption model and resulted in very similar Freundlich exponents (n=0.9), indicating slightly non-linear behavior. Results show that the influence of Ca(2+) compared to Na(+) is more pronounced. A logarithmic correlation between the Freundlich coefficient K(Fr) and the concentration or activity of the competing inorganic ions was found allowing the prediction of metoprolol sorption on the investigated sediment at different electrolyte concentrations. Additionally, the organic carbon of the sediment was completely removed for investigating the influence of organic matter on the sorption of metoprolol. The comparison between the experiments with and without organic carbon removal revealed no significant contribution of the organic carbon fraction (0.1%) to the sorption of metoprolol on the in this study investigated sediment. Results of this study will contribute to the development of predictive models for the transport of organic cations in the subsurface. Copyright © 2012 Elsevier Ltd. All rights reserved.

The effect of mineral composition on the sorption of cesium ions on geological formations.

PubMed

Kónya, József; Nagy, Noémi M; Nemes, Zoltán

2005-10-15

The sorption of cesium-137 on rock samples, mainly on clay rocks, is determined as a function of the mineral composition of the rocks. A relation between the mineral groups (tectosilicates, phyllosilicates, clay minerals, carbonates) and their cesium sorption properties is shown. A linear model is constructed by which the distribution coefficients of the different minerals can be calculated from the mineral composition and the net distribution coefficient of the rock. On the basis of the distribution coefficients of the minerals the cesium sorption properties of other rocks can be predicted.

Interaction of gases with ablative composites. I - Ar, CO2, and N2

NASA Technical Reports Server (NTRS)

King, C. A.; Wightman, J. P.

1974-01-01

The sorption of argon, carbon dioxide, and nitrogen on two heat shield composites (SLA-561 and SLA-561V) and on the SLA components was measured over the pressure range of 0.001 to 760 torr and in the temperature range of 30 to 50 C. The sorption of the gases by both the composites and the components varied directly with pressure. The sorption of CO2 by the phenolic spheres and the silicone elastomer and of Ar by the silicone elastomer varied inversely with temperature. The mechanism involved in the gas sorption was primarily absorption.

Cobalt sorption onto anaerobic granular sludge: isotherm and spatial localization analysis.

PubMed

van Hullebusch, Eric D; Gieteling, Jarno; Zhang, Min; Zandvoort, Marcel H; Daele, Wim Van; Defrancq, Jacques; Lens, Piet N L

2006-01-24

This study investigated the effect of different feeding regimes on the cobalt sorption capacity of anaerobic granular sludge from a full-scale bioreactor treating paper mill wastewater. Adsorption experiments were done with non-fed granules in monometal (only Co) and competitive conditions (Co and Ni in equimolar concentrations). In order to modify the extracellular polymeric substances and sulfides content of the granules, the sludge was fed for 30 days with glucose (pH 7, 30 degrees C, organic loading rate=1.2 g glucose l(-1) day-1) in the presence (COD/SO4(2-)=1) or absence of sulfate. The partitioning of the sorbed cobalt between the exchangeable, carbonates, organic matter/sulfides and residual fractions was determined using a sequential extraction procedure (modified Tessier). Experimental equilibrium sorption data for cobalt were analysed by the Langmuir, Freundlich and Redlich-Peterson isotherm equations. The total Langmuir maximal sorption capacity of the sludge fed with glucose and sulfate loaded with cobalt alone displayed a significantly higher maximal cobalt sorption (Qmax =18.76 mg g-1 TSS) than the sludge fed with glucose alone (Qmax =13.21 mg g-1 TSS), essentially due to an increased sorption capacity of the exchangeable (30-107%) and organic/sulfides fractions (70-30%). Environmental scanning electron microscopy coupled with an energy dispersive X-ray analysis of granular cross-sections showed that mainly iron minerals (i.e. iron sulfides) were involved in the cobalt accumulation. Moreover, the sorbed cobalt was mainly located at the edge of the granules. The sorption characteristics of the exchangeable and carbonates fractions fitted well to the Redlich-Peterson model (intermediate multi-layer sorption behaviour), whereas the sorption characteristics of the organic matter/sulfides and residual fractions fitted well to the Langmuir model (monolayer sorption behaviour). The organic matter/sulfides fraction displayed the highest affinity for cobalt for the three sludge types investigated.

Effect of pyrolysis temperature on polycyclic aromatic hydrocarbons toxicity and sorption behaviour of biochars prepared by pyrolysis of paper mill effluent treatment plant sludge.

PubMed

Devi, Parmila; Saroha, Anil K

2015-09-01

The polycyclic aromatic hydrocarbons (PAHs) toxicity and sorption behaviour of biochars prepared from pyrolysis of paper mill effluent treatment plant (ETP) sludge in temperature range 200-700 °C was studied. The sorption behaviour was found to depend on the degree of carbonization where the fractions of carbonized and uncarbonized organic content in the biochar act as an adsorption media and partition media, respectively. The sorption and partition fractions were quantified by isotherm separation method and isotherm parameters were correlated with biochar properties (aromaticity, polarity, surface area, pore volume and ash content). The risk assessment for the 16 priority EPA PAHs present in the biochar matrix was performed and it was found that the concentrations of the PAHs in the biochar were within the permissible limits prescribed by US EPA (except BC400 and BC500 for high molecular weight PAHs). Copyright © 2015 Elsevier Ltd. All rights reserved.

Effect of Cosolutes on the Sorption of Phenanthrene onto Mineral Surface of River Sediments and Kaolinite

PubMed Central

2014-01-01

Sorption of phenanthrene onto the natural sediment with low organic carbon content (OC%), organic-free sediment, and kaolinite was investigated through isotherm experiments. Effects of cosolutes (pyrene, 4-n-nonyphenol (NP), and humic acid (HA)) on phenanthrene sorption were also studied by comparing apparent solid-water distribution coefficients (K d app) of phenanthrene. Two addition sequences, including “cosolute added prior to phenanthrene” and “cosolute and phenanthrene added simultaneously,” were adopted. The Freundlich model fits phenanthrene sorption on all 3 sorbents well. The sorption coefficients on these sorbents were similar, suggesting that mineral surface plays an important role in the sorption of hydrophobic organic contaminants on low OC% sediments. Cosolutes could affect phenanthrene sorption on the sorbents, which depended on their properties, concentrations, and addition sequences. Pyrene inhibited phenanthrene sorption. Sorbed NP inhibited phenanthrene sorption at low levels and promoted sorption at high levels. Similar to NP, effect of HA on phenanthrene sorption onto the natural sediment depended on its concentrations, whereas, for the organic-free sediment and kaolinite, preloading of HA at high levels led to an enhancement in phenanthrene K d app while no obvious effect was observed at low HA levels; dissolved HA could inhibit phenanthrene sorption on the two sorbents. PMID:25147865

Glyphosate sorption/desorption on biochars – Interactions of physical and chemical processes

USDA-ARS?s Scientific Manuscript database

BACKGROUND: Biochar, a carbon-rich product of biomass pyrolysis, could limit glyphosate transport in soil and remediate contaminated water. The present study investigates the sorption/desorption behavior of glyphosate on biochars prepared from different hardwoods at temperatures ranging from 350°C t...

SORPTION, DIFFUSION AND PERMEATION OF 1,1,1- TRICHLOROETHANE THROUGH ADSORBENT-FILLED POLYMERIC MEMBRANES

EPA Science Inventory

Addition of hydrophobic absorbents such as activated carbon into polymeric mebranes increased the sorption capacity for 1,1,1-trichloroethane premeability of the mebranes used in the Pervaporation mode. Water permeability also increased for all filled membranes due to increased w...

Design Models for the Development of Helium-Carbon Sorption Crycoolers

NASA Technical Reports Server (NTRS)

Lindensmith, C. A.; Ahart, M.; Bhandari, P.; Wade, L. A.; Paine, C. G.

2000-01-01

We have developed models for predicting the performance of helium-based Joule-Thomson continuous-flow cryocoolers using charcoal-pumped sorption compressors. The models take as inputs the number of compressors, desired heat-lift, cold tip temperature, and available precooling temperature and provide design parameters as outputs. Future laboratory development will be used to verify and improve the models. We will present a preliminary design for a two-stage vibration-free cryocooler that is being proposed as part of a mid-infrared camera on NASA's Next Generation Space Telescope. Model predictions show that a 10 mW helium-carbon cryocooler with a base temperature of 5.5 K will reject less than 650 mW at 18 K. The total input power to the helium-carbon stage is 650 mW. These models, which run in MathCad and Microsoft Excel, can be coupled to similar models for hydrogen sorption coolers to give designs for 2-stage vibration-free cryocoolers that provide cooling from approx. 50 K to 4 K.

Design Models for the Development of Helium-Carbon Sorption Cryocoolers

NASA Technical Reports Server (NTRS)

Lindensmith, Chris A.; Ahart, M.; Bhandari, P.; Wade, L. A.; Paine, C. G.

2000-01-01

We have developed models for predicting the performance of helium-based Joule-Thomson continuous-flow cryocoolers using charcoal-pumped sorption compressors. The models take as inputs the number of compressors, desired heat-lift, cold tip temperature, and available precooling temperature and provide design parameters as outputs. Future laboratory development will be used to verify and improve the models. We will present a preliminary design for a two-stage vibration-free cryocooler that is being proposed as part of a mid-infrared camera on NASA's Next Generation Space Telescope. Model predictions show that a 10 mW helium-carbon cryocooler with a base temperature of 5.5 K will reject less than 650 mW at 18 K. The total input power to the helium-carbon stage is 650 mW. These models, which run in MathCad and Microsoft Excel, can be coupled to similar models for hydrogen sorption coolers to give designs for 2-stage vibration-free cryocoolers that provide cooling from approximately 50 K to 4 K.

Sorption of chlorobenzenes to cape cod aquifer sediments

USGS Publications Warehouse

Barber, L.B.

1994-01-01

Sorption of tetra- and pentachlorobenzene by sediment from a glacial outwash aquifer on Cape Cod, MA, was evaluated. Particle size and mineralogical fractions (separated based on paramagnetic susceptibility) were characterized with respect to sediment organic carbon (SOC), mineralogy, surface area, metal oxide coatings, and spatial variability. SOC increases by a factor of 10 as particle size decreases from 500-1000 to ?? 25 % in the <63-??m fraction, and SOC is preferentially associated with the magnetic minerals. Sorption increases with decreasing particle size (increasing SOC, magnetic minerals, surface area, and metal oxyhydroxides), and the magnetic mineral fraction has greater sorption than the bulk or nonmagnetic fractions. Removal of SOC decreases sorption proportional to the decrease in SOC and results in a nonlinear isotherm.

Quantitative structure property relationships for the adsorption of pharmaceuticals onto activated carbon.

PubMed

Dickenson, E R V; Drewes, J E

2010-01-01

Isotherms were determined for the adsorption of five pharmaceutical residues, primidone, carbamazepine, ibuprofen, naproxen and diclofenac, to Calgon Filtrasorb 300 powdered activated carbon (PAC). The sorption behavior was examined in ultra-pure and wastewater effluent organic matter (EfOM) matrices, where more sorption was observed in the ultra-pure water for PAC doses greater than 10 mg/L suggesting the presence of EfOM hinders the sorption of the pharmaceuticals to the PAC. Adsorption behaviors were described by the Freundlich isotherm model. Quantitative structure property relationships (QSPRs) in the form of polyparameter linear solvation energy relationships were developed for simulating the Freundlich adsorption capacity in both ultra-pure and EfOM matrices. The significant 3D-based descriptors for the QSPRs were the molar volume, polarizability and hydrogen-bond donor parameters.

Removal of metals from landfill leachate by sorption to activated carbon, bone meal and iron fines.

PubMed

Modin, Hanna; Persson, Kenneth M; Andersson, Anna; van Praagh, Martijn

2011-05-30

Sorption filters based on granular activated carbon, bone meal and iron fines were tested for their efficiency of removing metals from landfill leachate. Removal of Al, As, Ca, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Mo, Ni, Pb, Sr and Zn were studied in a laboratory scale setup. Activated carbon removed more than 90% of Co, Cr, Cu, Fe, Mn and Ni. Ca, Pb, Sr and Zn were removed but less efficiently. Bone meal removed over 80% of Cr, Fe, Hg, Mn and Sr and 20-80% of Al, Ca, Cu, Mo, Ni, Pb and Zn. Iron fines removed most metals (As, Ca, Co, Cr, Cu, Fe, Mg, Mn, Pb, Sr and Zn) to some extent but less efficiently. All materials released unwanted substances (metals, TOC or nutrients), highlighting the need to study the uptake and release of a large number of compounds, not only the target metals. To remove a wide range of metals using these materials two or more filter materials may need to be combined. Sorption mechanisms for all materials include ion exchange, sorption and precipitation. For iron fines oxidation of Fe(0) seems to be important for metal immobilisation. Copyright © 2011 Elsevier B.V. All rights reserved.

Sorption of mercury onto waste material derived low-cost activated carbon

NASA Astrophysics Data System (ADS)

Bhakta, Jatindra N.; Rana, Sukanta; Lahiri, Susmita; Munekage, Yukihiro

2017-03-01

The present study was performed to develop the low-cost activated carbon (AC) from some waste materials as potential mercury (Hg) sorbent to remove high amount of Hg from aqueous phase. The ACs were prepared from banana peel, orange peel, cotton fiber and paper wastes by pyrolysis and characterized by analyzing physico-chemical properties and Hg sorption capacity. The Brunauer Emmett and Teller surface areas (cotton 138 m2/g; paper 119 m2/g), micropore surface areas (cotton 65 m2/g; paper 54 m2/g) and major constituent carbon contents (cotton 95.04 %; paper 94.4 %) were higher in ACs of cotton fiber and paper wastes than the rest two ACs. The Hg sorption capacities and removal percentages were greater in cotton and paper wastes-derived ACs compared to those of the banana and orange peels. The results revealed that elevated Hg removal ability of cotton and paper wastes-derived ACs is largely regulated by their surface area, porosity and carbon content properties. Therefore, ACs of cotton and paper wastes were identified as potential sorbent among four developed ACs to remove high amount of Hg from aqueous phase. Furthermore, easily accessible precursor material, simple preparation process, favorable physico-chemical properties and high Hg sorption capacity indicated that cotton and paper wastes-derived ACs could be used as potential and low-cost sorbents of Hg for applying in practical field to control the severe effect of Hg contamination in the aquatic environment to avoid its human and environmental health risks.

Sorption and Release of Organics by Primary, Anaerobic, and Aerobic Activated Sludge Mixed with Raw Municipal Wastewater

PubMed Central

Modin, Oskar; Saheb Alam, Soroush; Persson, Frank; Wilén, Britt-Marie

2015-01-01

New activated sludge processes that utilize sorption as a major mechanism for organics removal are being developed to maximize energy recovery from wastewater organics, or as enhanced primary treatment technologies. To model and optimize sorption-based activated sludge processes, further knowledge about sorption of organics onto sludge is needed. This study compared primary-, anaerobic-, and aerobic activated sludge as sorbents, determined sorption capacity and kinetics, and investigated some characteristics of the organics being sorbed. Batch sorption assays were carried out without aeration at a mixing velocity of 200 rpm. Only aerobic activated sludge showed net sorption of organics. Sorption of dissolved organics occurred by a near-instantaneous sorption event followed by a slower process that obeyed 1st order kinetics. Sorption of particulates also followed 1st order kinetics but there was no instantaneous sorption event; instead there was a release of particles upon mixing. The 5-min sorption capacity of activated sludge was 6.5±10.8 mg total organic carbon (TOC) per g volatile suspend solids (VSS) for particulate organics and 5.0±4.7 mgTOC/gVSS for dissolved organics. The observed instantaneous sorption appeared to be mainly due to organics larger than 20 kDa in size being sorbed, although molecules with a size of about 200 Da with strong UV absorbance at 215–230 nm were also rapidly removed. PMID:25768429

Trihalomethane formation potential of aquatic and terrestrial fulvic and humic acids: Sorption on activated carbon.

PubMed

Abouleish, Mohamed Y Z; Wells, Martha J M

2015-07-15

Humic substances (HSs) are precursors for the formation of hazardous disinfection by-products (DBPs) during chlorination of water. Various surrogate parameters have been used to investigate the generation of DBPs by HS precursors and the removal of these precursors by activated carbon treatment. Dissolved organic carbon (DOC)- and ultraviolet absorbance (UVA254)-based isotherms are commonly reported and presumed to be good predictors of the trihalomethane formation potential (THMFP). However, THMFP-based isotherms are rarely published such that the three types of parameters have not been compared directly. Batch equilibrium experiments on activated carbon were used to generate constant-initial-concentration sorption isotherms for well-characterized samples obtained from the International Humic Substances Society (IHSS). HSs representing type (fulvic acid [FA], humic acid [HA]), origin (aquatic, terrestrial), and geographical source (Nordic, Suwannee, Peat, Soil) were examined at pH6 and pH9. THMFP-based isotherms were generated and compared to determine if DOC- and UVA254-based isotherms were good predictors of the THMFP. The sorption process depended on the composition of the HSs and the chemical nature of the activated carbon, both of which were influenced by pH. Activated carbon removal of THM-precursors was pH- and HS-dependent. In some instances, the THMFP existed after UVA254 was depleted. Copyright © 2015 Elsevier B.V. All rights reserved.

Effective use of iron-aluminum rich laterite based soil mixture for treatment of landfill leachate.

PubMed

Nayanthika, I V K; Jayawardana, D T; Bandara, N J G J; Manage, P M; Madushanka, R M T D

2018-04-01

Landfill leachate poses environmental threats worldwide and causes severe issues on adjacent water bodies and soil by direct discharge. The primary objective of this study is to analyze the efficient use of compost and laterite mixtures (0, 10, 20, 30 and 40 wt% compost/laterite) on leachate treatment and to investigate the associated removal efficiencies under different sorption processes. Therefore, in the experimental design, laterite is used for providing adsorption characteristics, and compost for activating biological properties of the filter. The filtering process is continued until major physical changes occur in the filter at approximately 100 days. The raw leachate used for the experiment shows higher average values for many analyzed parameters. Parameters for the experiment are selected based on their availability in raw leachate in the Sri Lanka. During filtering, removal efficiencies of BOD (>90%), COD (>85%), phosphate (>90%) and nitrate (75-95%) show higher values for all filters. These removals are mainly associated with biodegradation, which is activated by the added compost. Perhaps the removal of nitrate steadily increases with time, which indicates in denitrification by the added excess carbon from the leachate. The removal of total suspended solids (TSS) is moderate to high, but conversely, the electric conductivity (EC) is unsteady, indicating an association between iron exchange and carbonate degradation. A very high removal efficiency is reported in Fe (90-100%), and wide ranges of efficiencies in Mn (30-90%), Cu (45-85%), Ni (30-93%), Cd (37-98%), Zn (15-98%), and Pb (35-98%) involve heterogeneous sorption processes. Furthermore, the normalization of raw leachate by the liquid filtrate has apparent improvements. The differences (p > .05) in removal efficiencies between the filters are significant. It can be concluded that the filter with laterite mixed with 20% of compost has the optimum conditions. Further, the Fourier-transforminfrared (FT-IR) models for filter media conclude multiple sorptions and reveal evidence on vacant sites. X-ray diffraction (XRD) analyses indicate secondary minerals gibbsite, hematite, goethite and kaolinite as the major minerals that involved on the sorption process. Copyright © 2018 Elsevier Ltd. All rights reserved.

Role of Resuspended Sediments in the Transport and Bioaccumulation of Toxic Organic Contaminants in the Nearshore Marine Environment

DTIC Science & Technology

1994-10-11

predictions for the resuspended BRH sediments is not known but would be explained by another pool of sorption stibstrate acting to make up the difference...wo.ad lie in the presence of other active surfaces in addition to the organic carbon; it is possible that sorption onto mineral surfaces may be an...HOCs in the Great Lakes (Baker et al., 1986). Under conditions with a surplus of active sorption sites, the thermodynamic partition coefficient should

Batch-Versuche zur Bestimmung der Sorption und Reaktionskinetik von fluoreszierenden Tracern

NASA Astrophysics Data System (ADS)

Vaitl, Tobias; Wohnlich, Stefan

2018-06-01

For many tracer experiments, prior determination of interaction between solid medium and used tracers is of major interest in order to achieve efficient, economic and successful field experiments. In the present study, three different types of batch experiments were performed with three fluorescent dyes (Na-Fluorescein, Amidorhodamin G and Tinopal CBS-X) and three different rock types (sandstone, claystone and limestone), to determine distribution coefficients and reaction kinetics. All three rock types were analysed for organic carbon content, specific surface area and mineralogical composition to identify the main sorption mechanisms. For all tracers, different sorption properties were found depending on the type of rock. The strongest sorption was observed for Tinopal CBS-X in contact with claystone. Only Na-Fluorescein showed sorption (albeit limited) in contact with the sandstones. The investigated limestones indicated a high sorption for the tracer Tinopal CBS-X. Regarding reaction kinetics, in most cases, thermodynamic equilibrium conditions were reached after two weeks.

Influence of the isomerism on the sorption of imazamethabenz-methyl by soil.

PubMed

Pinna, Maria Vittoria; Pusino, Alba

2013-04-01

The sorption of meta and para isomers of the herbicide imazamethabenz-methyl, methyl 6-[(RS)-4-isopropyl-4-methyl-5-oxo-2-imidazolin-2-yl]-m- or p-toluate, by three soils and soil organic matter, was studied. Sorption isotherms conformed to the Freundlich equation. It was found that pH was the main factor influencing the adsorption in all of the systems. The highest level of sorption was measured on soils with low pH and high organic carbon content. Moreover, at low pH value, the soil rich in smectite clays, favoured the sorption of meta rather than para isomer. The higher affinity of clay surfaces for the meta isomer of the herbicide is due to the stabilization of the meta protonated form by resonance. At all pH values, the sorption on soil organic matter did not differ between two isomers. Copyright © 2012 Elsevier Ltd. All rights reserved.

Role of Inherent Inorganic Constituents in SO2 Sorption Ability of Biochars Derived from Three Biomass Wastes.

PubMed

Xu, Xiaoyun; Huang, Daxuan; Zhao, Ling; Kan, Yue; Cao, Xinde

2016-12-06

Biochar is rich in both organic carbon and inorganic components. Extensive work has attributed the high sorption ability of biochar to the pore structure and surface chemical property related to its organic carbon fraction. In this study, three biochars derived from dairy manure (DM-biochar), sewage sludge (SS-biochar), and rice husk (RH-biochar), respectively, were evaluated for their SO 2 sorption behavior and the underlying mechanisms, especially the role of inherent inorganic constituents. The sorption capacities of SO 2 by the three biochars were 8.87-15.9 mg g -1 . With the moisture content increasing from 0% to 50%, the sorption capacities increased by up to about 3 times, mainly due to the formation of alkaline water membrane on the biochar surface which could promote the sorption and transformation of acidic SO 2 . DM- and SS-biochar containing larger mineral constituents showed higher sorption capacity for SO 2 than RH-biochar containing less mineral components. CaCO 3 and Ca 3 (PO 4 ) 2 in DM-biochar induced sorbed SO 2 transformation into K 2 Ca(SO 4 ) 2 ·H 2 O and CaSO 4 ·2H 2 O, while the sorbed SO 2 was converted to Fe 2 (SO 4 ) 3 ·H 2 SO 4 ·2H 2 O, CaSO 4 ·2H 2 O, and Ca 3 (SO 3 ) 2 SO 4 ·12H 2 O in SS-biochar. For RH-biochar, K 3 H(SO 4 ) 2 might exist in the exhausted samples. Overall, the chemical transformation of SO 2 induced by biochar inherent mineral components occupied 44.6%-85.5% of the total SO 2 sorption. The results obtained from this study demonstrated that biochar as a unique carbonaceous material could distinctly be a promising sorbent for acidic SO 2 removal in which the inorganic components played an important role in the SO 2 sorption and transformation.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, S. H. D.; Kumar, R.; Krumpelt, M.

Methanol is considered to be a potential on-board fuel for fuel cell-powered vehicles. In current distribution systems for liquid fuels used in the transportation sector, commodity methanol can occasionally become contaminated with the sulfur in diesel fuel or gasoline. This sulfur would poison the catalytic materials used in fuel reformers for fuel cells. We tested the removal of this sulfur by means of ten activated carbons (AC) that are commercially available. Tests were conducted with methanol doped with 1 vol.% grade D-2 diesel fuel containing 0.29% sulfur, which was present essentially as 33-35 wt.% benzothiophenes (BTs) and 65-67 wt.% dibenzothiophenesmore » (DBT). In general, coconut shell-based carbons activated by high-temperature steam were more effective at sulfur removal than coal-based carbons. Equilibrium sorption data showed linear increase in sulfur capture with the increase of sulfur concentration in methanol. Both types of carbons had similar breakthrough characteristics, with the dynamic sorption capacity of each being about one-third of its equilibrium sorption capacity. Results of this study suggest that a fixed-bed sorber of granular AC can be used, such as in refueling stations, for the removal of sulfur in diesel fuel-contaminated methanol.« less

Application of headspace analysis to the study of sorption of hydrophobic organic chemicals to α-Al2O3

USGS Publications Warehouse

Pelinger, Judith A.; Eisenreich, Steven J.; Capel, Paul D.

1993-01-01

The sorption of hydrophobic organic chemicals (HOCs) to ??-Al2O3 was investigated with a headspace analysis method. The semiautomated headspace analyzer gave rapid, precise, and accurate results for a homologous series alkylbenzenes even at low percentages of solute mass sorbed (3-50%). Sorption experiments carried out with benzene alone indicated weak interactions with well-characterized aluminum oxide, and a solids concentration effect was observed. When the sorption coefficients for benzene alone obtained by headspace analysis were extrapolated up to the solids concentrations typically used in batch sorption experiments, the measured sorption coefficients agreed with reported sorption coefficients for HOCs and sediments of low fractional organic carbon content. Sorbed concentrations increased exponentially with aqueous concentration in isotherms with mixtures of alkylbenzenes, indicating solute-solute interactions at the mineral surface. Sorption was, however, greater than predicted for partitioning of a solute between its pure liquid phase and water, indicating additional influences of the surface and/or the structured liquid near the mineral surface. ?? 1993 American Chemical Society.

Geochemical heterogeneity in a sand and gravel aquifer: Effect of sediment mineralogy and particle size on the sorption of chlorobenzenes

USGS Publications Warehouse

Barber, Larry B.; Thurman, E. Michael; Runnells, Donald D.

1992-01-01

The effect of particle size, mineralogy and sediment organic carbon (SOC) on sorption of tetrachlorobenzene and pentachlorobenzene was evaluated using batch-isotherm experiments on sediment particle-size and mineralogical fractions from a sand and gravel aquifer, Cape Cod, Massachusetts. Concentration of SOC and sorption of chlorobenzenes increase with decreasing particle size. For a given particle size, the magnetic fraction has a higher SOC content and sorption capacity than the bulk or non-magnetic fractions. Sorption appears to be controlled by the magnetic minerals, which comprise only 5–25% of the bulk sediment. Although SOC content of the bulk sediment is <0.1%, the observed sorption of chlorobenzenes is consistent with a partition mechanism and is adequately predicted by models relating sorption to the octanol/water partition coefficient of the solute and SOC content. A conceptual model based on preferential association of dissolved organic matter with positively-charged mineral surfaces is proposed to describe micro-scale, intergranular variability in sorption properties of the aquifer sediments.

Typical agricultural diffuse herbicide sorption with agricultural waste-derived biochars amended soil of high organic matter content.

PubMed

Ouyang, Wei; Zhao, Xuchen; Tysklind, Mats; Hao, Fanghua

2016-04-01

Biochar application has been identified as the effective soil amendment and the materials to control the diffuse herbicide pollution. The atrazine was selected as the typical diffuse herbicide pollutant as the dominant proportion in applications. The biochar treated from four types of crops biomass were added to soil with high organic matter content. The basic sorption characteristics of biocahrs from corn cob (CC), corn stalk (CS), soybean straw (SS), rice straw (RS) and corn stalk paralyzed with 5% of ammonium dihydrogen phosphate (ACS) were analyzed, along with the comparison of the sorption difference of the raw soil and soil amended with biochars at four levels of ratio (0.5%, 1.0%, 3.0% and 5.0%). It was found that the linear distribution isotherm of raw soil was much effective due to the high organic matter background concentration. The addition of five types of biochars under two kinds of initial atrazine concentration (1 mg/L and 20 mg/L) demonstrated the sorption variances. Results showed the soil amended with RS and CS biochar had the biggest removal rate in four regular biochars and the removal rate of the ACS was the biggest. The sorption coefficient and the normalized sorption coefficient from Freundlich modeling presented the isothermal sorption characteristics of atrazine with soil of high organic matter content. The normalized sorption coefficient increased with the equilibrium concentration decreased in the biochar amended soil, which indicated the sorption performance will be better due to the low atrazine concentration in practice. Results showed that biochar amendment is the effective way to prevent leakage of diffuse herbicide loss. Copyright © 2016 Elsevier Ltd. All rights reserved.

Physical and chemical characterization of Devonian gas shale. Quarterly status report, October 1-December 31, 1978

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zielinski, R.E.; Nance, S.W.

On shale samples from the WV-6 (Monongalia County, West Virginia) well, mean total gas yield was 80.4 ft/sup 3//ton. Mean hydrocarbon gas yield was 5.7 ft/sup 3//ton, 7% of total yield. Methane was the major hydrocarbon component and carbon dioxide the major nonhydrocarbon component. Oil yield was negligible. Clay minerals and organic matter were the dominant phases of the shale. Illite averages 76% of the total clay mineral content. This is detrital illite. Permeation of methane, parallel to the bedding direction for select samples from WV-5 (Mason County, West Virginia) well ranges from 10/sup -4/ to 10/sup -12/ darcys. Themore » permeability of these shales is affected by orgaic carbon content, density, particle orientation, depositional facies, etc. Preliminary studies of Devonian shale methane sorption rates suggest that these rates may be affected by shale porosity, as well as absorption and adsorption processes. An experimental system was designed to effectively simulate sorption of methane at natural reservoir conditions. The bulk density and color of select shales from Illinois, Appalachian and Michigan Basins suggest a general trend of decreasing density with increasing organic content. Black and grayish black shales have organic contents which normally exceed 1.0 wt %. Medium dark gray and gray shales generally have organic contents less than 1.0 wt %.« less

Seamless Integration of Detection and Therapy for Breast Cancer using Targeted Engineered Nanoparticles

DTIC Science & Technology

2007-06-01

and exhibit strong scattering and ab- sorption effects due to the strong plasmon resonance of the metallic-dielectric concentric spherical...neglecting its ab- sorption properties. Thus, the studies will be further separated into two sets, one considering only the scattering properties of the... sorption from the gold nanoshells, the reflectance is more de- pendent on the volume-normalized absorption cross section than the combination of

Effects of human management on black carbon sorption/desorption during a water transfer project: Recognizing impacts and identifying mitigation possibilities.

PubMed

Hao, Rong; Zhang, Jinliang; Wang, Peichao; Hu, Ronggui; Song, Yantun; Wu, Yupeng; Qiu, Guohong

2018-05-15

Water resources management is an important public concern. In this study, we examined the extent of sorption/desorption of trace pollutants to soil black carbon (BC) in the water level fluctuation zone (WLFZ) of the middle route of the South to North Water Transfer Project in China. In addition, we investigated the main management measures affecting these processes during the project. The results showed that the pseudo second-order model adequately describes the sorption/desorption of phenanthrene on the soil BC in the WLFZ. Water level fluctuation may indirectly influenced BC sorption/desorption by altering water chemistry. Water level residence time had negative effects on BC sorption in short-term experiments (days to months), but the impact gradually diminished with increased residence time. The results suggested that long-term field monitoring of water chemistry is urgent. During the initial period of water transfer, delaying the water supplies as drinking water source or directly irrigating crops could mitigate the adverse impacts. Future research should focus on the water-soluble products of BC degradation. The findings of this study should be useful in improving sustainable management of water resources for water transfer projects. Copyright © 2018 Elsevier Ltd. All rights reserved.

Selective Solid-Phase Extraction of Zinc(II) from Environmental Water Samples Using Ion Imprinted Activated Carbon.

PubMed

Moniri, Elham; Panahi, Homayon Ahmad; Aghdam, Khaledeh; Sharif, Amir Abdollah Mehrdad

2015-01-01

A simple ion imprinted amino-functionalized sorbent was synthesized by coupling activated carbon with iminodiacetic acid, a functional compound for metal chelating, through cyanoric chloride spacer. The resulting sorbent has been characterized using FTIR spectroscopy, elemental analysis, and thermogravimetric analysis and evaluated for the preconcentration and determination of trace Zn(II) in environmental water samples. The optimum pH value for sorption of the metal ion was 6-7.5. The sorption capacity of the functionalized sorbent was 66.6 mg/g. The chelating sorbent can be reused for 10 cycles of sorption-desorption without any significant change in sorption capacity. A recovery of 100% was obtained for the metal ion with 0.5 M nitric acid as the eluent. Compared with nonimprinted polymer particles, the prepared Zn-imprinted sorbent showed high adsorption capacity, significant selectivity, and good site accessibility for Zn(II). Scatchard analysis revealed that the homogeneous binding sites were formed in the polymer. The equilibrium sorption data of Zn(II) by modified resin were analyzed by Langmuir, Freundlich, Temkin, and Redlich-Peterson models. Based on equilibrium adsorption data, the Langmuir, Freundlich, and Temkin constants were determined as 0.139, 12.82, and 2.34, respectively, at 25°C.

Adsorption of Carbon Dioxide, Ammonia, Formaldehyde, and Water Vapor on Regenerable Carbon Sorbents

NASA Technical Reports Server (NTRS)

Wojtowicz, Marek A.; Cosgrove, Joseph E.; Serio, Michael A.; Wilburn, Monique

2015-01-01

Results are presented on the development of reversible sorbents for the combined carbon dioxide, moisture, and trace-contaminant (TC) removal for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). The currently available life support systems use separate units for carbon dioxide, trace contaminants, and moisture control, and the long-term objective is to replace the above three modules with a single one. Furthermore, the current TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal, which is nonregenerable, and the carbon-based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. In this study, several carbon sorbents were fabricated and tested for simultaneous carbon dioxide, ammonia, formaldehyde, and water sorption. Multiple adsorption/vacuum-regeneration cycles were demonstrated at room temperature, and also the enhancement of formaldehyde sorption by the presence of ammonia in the gas mixture.

Highly porous carbon from a natural cellulose fiber as high efficiency sorbent for lead in waste water.

PubMed

Ilangovan, Manikandan; Guna, Vijaykumar; Olivera, Sharon; Ravi, Ashwini; Muralidhara, H B; Santosh, M S; Reddy, Narendra

2017-12-01

The persistence of hollow centre in the carbon obtained from milkweed floss provides exceptional sorption characteristics, not seen in common biomasses or their derivatives. A considerably high sorption of 320mg of lead per gram of milkweed carbon was achieved without any chemical modification to the biomass. In this research, we have carbonized milkweed floss and used the carbon as a sorbent for lead in waste water. A high surface area of 170m 2 g -1 and pore volume of 1.07cm 3 g -1 was seen in the carbon. Almost complete removal (>99% efficiency) of lead could be achieved within 5min when the concentration of lead in the solution was 100ppm, close to that prevailing in industrial waste water. SEM images showed that the carbon was hollow and confocal images confirmed that the sorbate could penetrate inside the hollow tube. Copyright © 2017 Elsevier Ltd. All rights reserved.

Three-dimensional iron(ii) porous coordination polymer exhibiting carbon dioxide-dependent spin crossover.

PubMed

Shin, Jong Won; Jeong, Ah Rim; Jeoung, Sungeun; Moon, Hoi Ri; Komatsumaru, Yuki; Hayami, Shinya; Moon, Dohyun; Min, Kil Sik

2018-04-24

We report a three-dimensional Fe(ii) porous coordination polymer that exhibits a spin crossover temperature change following CO2 sorption (though not N2 sorption). Furthermore, single crystals of the desolvated polymer with CO2 molecules at three different temperatures were characterised by X-ray crystallography.

SORPTION OF 2,3,7,8-TETRACHLORODIBENZO-P-DIOXIN TO SOILS FROM WATER/METHANOL MIXTURES

EPA Science Inventory

Sorption of ¹⁴C-labeled 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) to soils from water/methanol mixtures has been evaluated by batch shake testing. Uncontaminated soils from Times Beach, MO, were used in these experiments and ranged in fraction organic carbon (U...

Nano-rod Ca-decorated sludge derived carbon for removal of phosphorus.

PubMed

Kong, Lingjun; Han, Meina; Shih, Kaimin; Su, Minhua; Diao, Zenghui; Long, Jianyou; Chen, Diyun; Hou, Li'an; Peng, Yan

2018-02-01

Recovering phosphorus (P) from waste streams takes the unique advantage in simultaneously addressing the crisis of eutrophication and the shortage of P resource. A novel calcium decorated sludge carbon (Ca-SC) was developed from dyeing industry wastewater treatment sludge by decorating calcium (Ca) to effectively adsorb phosphorus from solution. The X-ray diffraction (XRD) and Fourier transform infrared (FTIR) techniques were used to characterize the Ca-SCs, followed by isotherm and kinetic sorption experiments. A preferred design with CaCO 3 to sludge mass ratio of 1:2 was found to have a sorption capacity of 116.82 mg/g for phosphorus. This work reveals the crucial role of well-dispersed nano-rod calcium on the Ca-SC surface for the sorption of phosphorus. Moreover, the decoration of nano-rod calcium was found to further promote the uptake of phosphorus through the formation of hydroxylapatite (Ca 5 (PO 4 ) 3 (OH)). Thus, the development of decorated Ca-SC for sorption of phosphorus is very important in solving the P pollution and resource loss. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorbents with high efficiency for CO2 capture based on amines-supported carbon for biogas upgrading.

PubMed

Pino, Lidia; Italiano, Cristina; Vita, Antonio; Fabiano, Concetto; Recupero, Vincenzo

2016-10-01

Sorbents for CO 2 capture have been prepared by wet impregnation of a commercial active carbon (Ketjen-black, Akzo Nobel) with two CO 2 -philic compounds, polyethylenimine (PEI) and tetraethylenepentamine (TEPA), respectively. The effects of amine amount (from 10 to 70wt.%), CO 2 concentration in the feed, sorption temperature and gas hourly space velocity on the CO 2 capture performance have been investigated. The sorption capacity has been evaluated using the breakthrough method, with a fixed bed reactor equipped with on line gas chromatograph. The samples have been characterized by N 2 adsorption-desorption, scanning electron microscopy and energy dispersive X-ray (SEM/EDX). A promising CO 2 sorption capacity of 6.90 mmol/g sorbent has been obtained with 70wt.% of supported TEPA at 70°C under a stream containing 80vol% of CO 2 . Sorption tests, carried out with simulated biogas compositions (CH 4 /CO 2 mixtures), have revealed an appreciable CO 2 separation selectivity; stable performance was maintained for 20 adsorption-desorption cycles. Copyright © 2016. Published by Elsevier B.V.

Impacts of compound properties and sediment characteristics on the sorption behaviour of pharmaceuticals in aquatic systems.

PubMed

Al-Khazrajy, Omar S A; Boxall, Alistair B A

2016-11-05

Sorption is a key factor in determining the persistence, attenuation and bioavailability of sediment-associated contaminants. However, our understanding of the sorption behaviour of pharmaceuticals in sediments is poor. In this study, we investigated the sorption behaviour of a diverse set of pharmaceuticals in a range sediment types. Sorption affinity of pharmaceuticals for all sediments was found to increase in the order mefenamic acid

Organo-mineral complexation alters carbon and nitrogen cycling in stream microbial assemblages

NASA Astrophysics Data System (ADS)

Hunter, William Ross; Wanek, Wolfgang; Prommer, Judith; Mooshammer, Maria; Battin, Tom

2014-05-01

Inland waters are of global biogeochemical importance receiving carbon inputs of ~ 4.8 Pg C y-1. Of this 12 % is buried, 18 % transported to the oceans, and 70 % supports aquatic secondary production. However, the mechanisms that determine the fate of organic matter (OM) in these systems are poorly defined. One important aspect is the formation of organo-mineral complexes in aquatic systems and their potential as a route for OM transport and burial vs. microbial utilization as organic carbon (C) and nitrogen (N) sources. Organo-mineral particles form by sorption of dissolved OM to freshly eroded mineral surfaces and may contribute to ecosystem-scale particulate OM fluxes. We tested the availability of mineral-sorbed OM as a C & N source for streamwater microbial assemblages and streambed biofilms. Organo-mineral particles were constructed in vitro by sorption of 13C:15N-labelled amino acids to hydrated kaolin particles, and microbial degradation of these particles compared with equivalent doses of 13C:15N-labelled free amino acids. Experiments were conducted in 120 ml mesocosms over 7 days using biofilms and streamwater sampled from the Oberer Seebach stream (Austria), tracing assimilation and mineralization of 13C and 15N labels from mineral-sorbed and dissolved amino acids. Here we present data on the effects of organo-mineral sorption upon amino acid mineralization and its C:N stoichiometry. Organo-mineral sorption had a significant effect upon microbial activity, restricting C and N mineralization by both the biofilm and streamwater treatments. Distinct differences in community response were observed, with both dissolved and mineral-stabilized amino acids playing an enhanced role in the metabolism of the streamwater microbial community. Mineral-sorption of amino acids differentially affected C & N mineralization and reduced the C:N ratio of the dissolved amino acid pool. The present study demonstrates that organo-mineral complexes restrict microbial degradation of OM and may, consequently, alter the carbon and nitrogen cycling dynamics within aquatic ecosystems.

Pesticide interactions with soil affected by olive mill wastewater (OMW): how strong and long-lasting is the OMW effect?

NASA Astrophysics Data System (ADS)

Keren, Yonatan; Borisover, Mikhail; Schaumann, Gabriele E.; Diehl, Dörte; Tamimi, Nisreen; Bukhanovsky, Nadezhda

2017-04-01

Sorption interactions with soils are well known to control the environmental fate of multiple organic compounds including pesticides. Pesticide-soil interactions may be affected by organic amendments or organic matter (OM)-containing wastewater brought to the field. Specifically, land spreading of olive mill wastewater (OMW), occurring intentionally or not, may also influence pesticide-soil interactions. The effects of the OMW disposed in the field on soil properties, including their ability to interact with pesticides, become of great interest due to the increasing demand for olive oil and a constant growth of world oil production. This paper summarizes some recent findings related to the effect of prior OMW land application on the ability of soils to interact with the organic compounds including pesticides, diuron and simazine. The major findings are as following: (1) bringing OMW to the field increases the potential of soils to sorb non-ionized pesticides; (2) this sorption increase may not be related solely to the increase in soil organic carbon content but it can reflect also the changes in the soil sorption mechanisms; (3) increased pesticide interactions with OMW-affected soils may become irreversible, due, assumedly, to the swelling of some components of the OMW-treated soil; (4) enhanced pesticide-soil interactions mitigate with the time passed after the OMW application, however, in the case of diuron, the remaining effect could be envisioned at least 600 days after the normal OMW application; (5) the enhancement effect of OMW application on soil sorption may increase with soil depth, in the 0-10 cm interval; (6) at higher pesticide (diuron) concentrations, larger extents of sorption enhancement, following the prior OMW-soil interactions, may be expected; (7) disposal of OMW in the field may be seasonal-dependent, and, in the case studied, it led to more distinct impacts on sorption when carried out in spring and winter, as compared with summer. It appears that when examining the fate of organic compounds in soil environments affected by OMW, more attention is needed to (a) the effect of the OMW penetration into the depth on soil-pesticide interactions; (b) long-term and seasonal-dependent effects of OMW application.

Adsorption of sulfamethoxazole and sulfapyridine antibiotics in high organic content soils.

PubMed

Chen, Kuen-Lin; Liu, Li-Chun; Chen, Wan-Ru

2017-12-01

Many antibiotics, including sulfonamides, are being frequently detected in soil and groundwater. Livestock waste is an important source of antibiotic pollution, and sulfonamides may be present along with organic-rich substances. This study aims to investigate the sorption reaction of two sulfonamides, sulfamethoxazole (SMZ) and sulfapyridine (SPY) in two organic-rich sorbents: a commercial peat soil (38.41% carbon content) and a composted manure (24.33% carbon content). Batch reactions were conducted to evaluate the impacts of pH (4.5-9.5) and background ions (0.001 M-0.1 M CaCl 2 ) on their sorption. Both linear partitioning and Freundlich sorption isotherms fit the reaction well. The n values of Freundlich isotherm were close to 1 in most conditions suggesting that the hydrophobic partition is the major adsorption mechanism. In terms of SMZ, K d declined with increases in the pH. SPY has a pyridine group that is responsible for adsorption at high pH values, and thus, no significant trend between K d and pH was observed. At high pH ranges, SPY sorption deviated significantly from linear partitioning. The results suggested the sorption mechanism of these two sulfonamide antibiotics tended to be hydrophobic partitioning under most of the experimental conditions, especially at pH values lower than their corresponding pK a2. The fluorescence excitation emission matrix and dissolved organic carbon leaching test suggested composted manure has higher fulvic acid organics and that peat soil has higher humus-like organics. Small organic molecules showed stronger affinity toward sulfonamide antibiotics and cause the composted manure to exhibit higher sorption capacity. Overall, this study suggests that the chemical structure and properties of sulfonamides antibiotics and the type of organic matter in soils will greatly influence the fate and transport of these contaminants into the environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

Retention and loss of water extractable carbon in soils: effect of clay properties.

PubMed

Nguyen, Trung-Ta; Marschner, Petra

2014-02-01

Clay sorption is important for organic carbon (C) sequestration in soils, but little is known about the effect of different clay properties on organic C sorption and release. To investigate the effect of clay content and properties on sorption, desorption and loss of water extractable organic C (WEOC), two experiments were conducted. In experiment 1, a loamy sand alone (native) or mixed with clay isolated from a surface or subsoil (78 and 96% clay) resulting in 90, 158 and 175 g clay kg(-1) soil. These soil treatments were leached with different WEOC concentrations, and then CO2 release was measured for 28 days followed by leaching with reverse osmosis water at the end of experiment. The second experiment was conducted to determine WEOC sorption and desorption of clays isolated from the loamy sand (native), surface soil and subsoil. Addition of clays isolated from surface and subsoil to sandy loam increased WEOC sorption and reduced C leaching and cumulative respiration in percentage of total organic C and WEOC added when expressed per g soil and per g clay. Compared to clays isolated from the surface and subsoil, the native clay had higher concentrations of illite and exchangeable Ca(2+), total organic C and a higher CEC but a lower extractable Fe/Al concentration. This indicates that compared to the clay isolated from the surface and the subsoil, the native clay had fewer potential WEOC binding sites because it had lower Fe/Al content thus lower number of binding sites and the existing binding sites are already occupied native organic matter. The results of this study suggest that in the soils used here, the impact of clay on WEOC sorption and loss is dependent on its indigenous organic carbon and Fe and/or Al concentrations whereas clay mineralogy, CEC, exchangeable Ca(2+) and surface area are less important. © 2013.

Evaluation of sewage sludge and slow pyrolyzed sewage sludge-derived biochar for adsorption of phenanthrene and pyrene.

PubMed

Zielińska, Anna; Oleszczuk, Patryk

2015-09-01

The present study investigated the sorption of phenanthrene (PHE) and pyrene (PYR) by sewage sludges and sewage sludge-derived biochars. The organic carbon normalized distribution coefficient (log K(OC) for C(w) = 0.01 S(w)) for the sewage sludges ranged from 5.62 L kg(-1) to 5.64 L kg(-1) for PHE and from 5.72 L kg(-1) to 5.75 L kg(-1) for PYR. The conversion of sewage sludges into biochar significantly increased their sorption capacity. The value of log K(OC) for the biochars ranged from 5.54 L kg(-1) to 6.23 L kg(-1) for PHE and from 5.95 L kg(-1) to 6.52 L kg(-1) for PYR depending on temperature of pyrolysis. The dominant process was monolayer adsorption in the micropores and/or multilayer surface adsorption (in the mesopores), which was indicated by the significant correlations between log K(OC) and surface properties of biochars. PYR was sorbed better on the tested materials than PHE. Copyright © 2015 Elsevier Ltd. All rights reserved.

Steady-state equation of water vapor sorption for CaCl2-based chemical sorbents and its application

PubMed Central

Zhang, Haiquan; Yuan, Yanping; Sun, Qingrong; Cao, Xiaoling; Sun, Liangliang

2016-01-01

Green CaCl2-based chemical sorbent has been widely used in sorption refrigeration, air purification and air desiccation. Methods to improve the sorption rate have been extensively investigated, but the corresponding theoretical formulations have not been reported. In this paper, a sorption system of solid-liquid coexistence is established based on the hypothesis of steady-state sorption. The combination of theoretical analysis and experimental results indicates that the system can be described by steady-state sorption process. The steady-state sorption equation, μ = (η − γT) , was obtained in consideration of humidity, temperature and the surface area. Based on engineering applications and this equation, two methods including an increase of specific surface area and adjustment of the critical relative humidity (γ) for chemical sorbents, have been proposed to increase the sorption rate. The results indicate that the CaCl2/CNTs composite with a large specific surface area can be obtained by coating CaCl2 powder on the surface of carbon nanotubes (CNTs). The composite reached sorption equilibrium within only 4 h, and the sorption capacity was improved by 75% compared with pure CaCl2 powder. Furthermore, the addition of NaCl powder to saturated CaCl2 solution could significantly lower the solution’s γ. The sorption rate was improved by 30% under the same environment. PMID:27682811

Steady-state equation of water vapor sorption for CaCl2-based chemical sorbents and its application

NASA Astrophysics Data System (ADS)

Zhang, Haiquan; Yuan, Yanping; Sun, Qingrong; Cao, Xiaoling; Sun, Liangliang

2016-09-01

Green CaCl2-based chemical sorbent has been widely used in sorption refrigeration, air purification and air desiccation. Methods to improve the sorption rate have been extensively investigated, but the corresponding theoretical formulations have not been reported. In this paper, a sorption system of solid-liquid coexistence is established based on the hypothesis of steady-state sorption. The combination of theoretical analysis and experimental results indicates that the system can be described by steady-state sorption process. The steady-state sorption equation, μ = (η - γT) , was obtained in consideration of humidity, temperature and the surface area. Based on engineering applications and this equation, two methods including an increase of specific surface area and adjustment of the critical relative humidity (γ) for chemical sorbents, have been proposed to increase the sorption rate. The results indicate that the CaCl2/CNTs composite with a large specific surface area can be obtained by coating CaCl2 powder on the surface of carbon nanotubes (CNTs). The composite reached sorption equilibrium within only 4 h, and the sorption capacity was improved by 75% compared with pure CaCl2 powder. Furthermore, the addition of NaCl powder to saturated CaCl2 solution could significantly lower the solution’s γ. The sorption rate was improved by 30% under the same environment.

Removal of perfluorinated surfactants from wastewater by adsorption and ion exchange - Influence of material properties, sorption mechanism and modeling.

PubMed

Schuricht, Falk; Borovinskaya, Ekaterina S; Reschetilowski, Wladimir

2017-04-01

Perfluorooctane sulfonate (PFOS) has attracted increasing concern in recent years due to its world-wide distribution, persistence, bioaccumulation and potential toxicity. The influence of sorbent properties on the adsorptive elimination of PFOS from wastewater by activated carbons, polymer adsorbents and anion exchange resins was investigated with regard to their isotherms and kinetics. The batch and column tests were combined with physicochemical characterization methods, e.g., N 2 physisorption, mercury porosimetry, infrared spectroscopy, differential scanning calorimetry, titrations, as well as modeling. Sorption kinetics was successfully modelled applying the linear driving force (LDF) approach for surface diffusion after introducing a load dependency of the mass transfer coefficient β s . The big difference in the initial mass transfer coefficient β s,0 , when non-functionalized adsorbents and ion-exchange resins are compared, suggests that the presence of functional groups impedes the intraparticle mass transport. The more functional groups a resin possesses and the longer the alkyl moieties are the bigger is the decrease in sorption rate. But the selectivity for PFOS sorption is increasing when the character of the functional groups becomes more hydrophobic. Accordingly, ion exchange and hydrophobic interaction were found to be involved in the sorption processes on resins, while PFOS is only physisorptively bound to activated carbons and polymer adsorbents. In agreement with the different adsorption mechanisms, resins possess higher total sorption capacities than adsorbents. Hence, the latter ones are rendered more effective in PFOS elimination at concentrations in the low μg/L range, due to a less pronounced convex curvature of the sorption isotherm in this concentration range. Copyright © 2016. Published by Elsevier B.V.

Sorption of lead from aqueous solution by chemically modified carbon adsorbents.

PubMed

Nadeem, Muhammad; Mahmood, A; Shahid, S A; Shah, S S; Khalid, A M; McKay, G

2006-12-01

An indigenously prepared, steam activated and chemically modified carbon from husk and pods of Moringa oleifera (M. oleifera), an agricultural waste, was comparatively examined as an adsorbent for the removal of lead from aqueous solutions. Studies were conducted as a function of contact time, initial metal concentration, dose of adsorbent, agitation speed, particle size and pH. Maximum uptake capacities were found to be, 98.89, 96.58, 91.8, 88.63, 79.43% for cetyltrimethyl ammonium bromide (CTAB), phosphoric, sulfuric, hydrochloric acid treated and untreated carbon adsorbents, respectively. Bangham, pseudo-first- and second-order, intra-particle diffusion equations were implemented to express the sorption mechanism by utilized adsorbents. Adsorption rate of lead ions was found to be considerably faster for chemically modified adsorbents than unmodified. The results of adsorption were fitted to both the Langmuir and Freundlich models. Satisfactory agreement between the metal uptake capacities by the adsorbents at different time intervals was expressed by the correlation coefficient (R(2)). The Langmuir model represented the sorption process better than the Freundlich one, with R(2) values ranging from 0.994 to 0.998.

Mobility of rare earth elements in mine drainage: Influence of iron oxides, carbonates, and phosphates.

PubMed

Edahbi, Mohamed; Plante, Benoît; Benzaazoua, Mostafa; Ward, Matthew; Pelletier, Mia

2018-05-01

The geochemical behavior of rare earth elements (REE) was investigated using weathering cells. The influence of sorption and precipitation on dissolved REE mobility and fractionation is evaluated using synthetic iron-oxides, carbonates, and phosphates. Sorption cell tests are conducted on the main lithologies of the expected waste rocks from the Montviel deposit. The sorbed materials are characterized using a scanning electron microscope (SEM) equipped with a microanalysis system (energy dispersive spectroscopy EDS) (SEM-EDS), X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) in order to understand the effect of the synthetic minerals on REE mobility. The results confirm that sorption and precipitation control the mobility and fractionation of REE. The main sorbent phases are the carbonates, phosphates (present as accessory minerals in the Montviel waste rocks), and iron oxides (main secondary minerals generated upon weathering of the Montviel lithologies). The XANES results show that REE are present as trivalent species after weathering. Thermodynamic equilibrium calculations results using Visual Minteq suggest that REE could precipitate as secondary phosphates (REEPO 4 ). Copyright © 2018 Elsevier Ltd. All rights reserved.

Organic Carbon--water Concentration Quotients (IIsocS and [pi]pocS): Measuring Apparent Chemical Disequilibria and Exploring the Impact of Black Carbon in Lake Michigan

EPA Science Inventory

When black carbon (bc) and biologically derived organic carbon (bioc) phases are present in sediments or suspended particulates, both forms of carbon act additively to sorb organic chemicals but the bc phase has more sorption capacity per unit mass. . . .

PEMFC catalyst layers: the role of micropores and mesopores on water sorption and fuel cell activity.

PubMed

Soboleva, Tatyana; Malek, Kourosh; Xie, Zhong; Navessin, Titichai; Holdcroft, Steven

2011-06-01

The effects of carbon microstructure and ionomer loading on water vapor sorption and retention in catalyst layers (CLs) of PEM fuel cells are investigated using dynamic vapor sorption. Catalyst layers based on Ketjen Black and Vulcan XC-72 carbon blacks, which possess distinctly different surface areas, pore volumes, and microporosities, are studied. It is found that pores <20 nm diameter facilitate water uptake by capillary condensation in the intermediate range of relative humidities. A broad pore size distribution (PSD) is found to enhance water retention in Ketjen Black-based CLs whereas the narrower mesoporous PSD of Vulcan CLs is shown to have an enhanced water repelling action. Water vapor sorption and retention properties of CLs are correlated to electrochemical properties and fuel cell performance. Water sorption enhances electrochemical properties such as the electrochemically active surface area (ESA), double layer capacitance and proton conductivity, particularly when the ionomer content is very low. The hydrophilic properties of a CL on the anode and the cathode are adjusted by choosing the PSD of carbon and the ionomer content. It is shown that a reduction of ionomer content on either cathode or anode of an MEA does not necessarily have a significant detrimental effect on the MEA performance compared to the standard 30 wt % ionomer MEA. Under operation in air and high relative humidity, a cathode with a narrow pore size distribution and low ionomer content is shown to be beneficial due to its low water retention properties. In dry operating conditions, adequate ionomer content on the cathode is crucial, whereas it can be reduced on the anode without a significant impact on fuel cell performance. © 2011 American Chemical Society

Effect of coexisting Al(III) ions on Pb(II) sorption on biochars: Role of pH buffer and competition.

PubMed

Yang, Yuxi; Zhang, Weihua; Qiu, Hao; Tsang, Daniel C W; Morel, Jean-Louis; Qiu, Rongliang

2016-10-01

Biochar is being widely considered as a promising amendment agent for immobilizing heavy metals in contaminated acidic soils, where plenty of soluble Al(III) ions exist. In view of uncertain significance of the effects of coexisting Al(III) on Pb(II) sorption by biochars, this study used kenaf core biochar (KB550; high carbon, low ash) and sewage sludge biochar (SB550; low carbon, high ash) pyrolyzed at 550 °C to elucidate the influence of coexisting Al(III) species and biochars' mineral components on Pb(II) immobilization conducted in aqueous solution with initial pHs of 3.0-4.5. Results showed that Al(III) reduced Pb(II) sorption on KB550 primarily via pH buffering against biochar alkalinity, thus inhibiting lead carbonate formation. In contrast, the reduction on SB550 mainly resulted from direct competition for sorption sites, especially on Fe-rich phengite 2M1 and metakaolinite. Because of Pb-P precipitation and Pb-K interlayer exchange, the residual Pb(II) adsorption capacity resistant to coexisting Al(III) was 3-5 times higher on SB550 than on KB550. The Pb-K interlayer exchange was enhanced by lower pH and coexisting Al(III), while Pb-P precipitation was the dominant Pb(II) sorption mechanism on SB550 resistant to Al(III) buffering and competition at higher pH. Application of these two biochars as amendments confirmed that the mineral-rich SB550 was more suitable for Pb(II) immobilization in acidic soils with high levels of extractable Al(III). Copyright © 2016 Elsevier Ltd. All rights reserved.

Carbonate component reduces o,oEDDHA/Fe sorption on two-line ferrihydrite

NASA Astrophysics Data System (ADS)

Yunta, F.; Lucena, J. J.; Smolders, E.

2012-04-01

The o,oEDDHA/Fe is the most common and effective iron chelate used as fertilizer in calcareous soils. Several authors have reported that the anionic o,oEDDHA/Fe complex is adsorbed to soil components such as ferrihydrite. The bicarbonate anion may be a competing ion for this sorption, however no studies have yet identified the extent and mechanism of this interaction. The aim of this work was to study the carbonate (bicarbonate + carbonate) effect on EDDHA/Fe adsorption on two-line ferrihydrite. Two-line ferrihydrite was synthetized adding NaOH on a nitrate iron (III) solution up to a final pH to be 8.0 and allowing to age for 22 hours at 20°C. Dialyzed ferrihydrite was characterized by determining specific parameters such as Fe/OH ratio, BET surface, point zero of charge and x-ray diffraction. The sorption was performed at three pH levels (5, 7.5 and 9.5) and three initial carbonate concentrations (from 0 to 2 mM). Initial EDDHA/Fe, ferrihydrite and ionic strength concentrations were adjusted to 0.18 mM, 10 g L-1 and 5 mM respectively. Total dissolved FeEDDHA concentrations were quantified at 480 nm. The o,oEDDHA/Fe isomers (rac-o,oEDDHA/Fe and meso-o,oEDDHA/Fe) were separated and quantified by High Performance Liquid Chromatography (HPLC) fitting a photodiode array detector (PDA). Distribution factor (KD) and sorbed o,oEDDHA/Fe concentration were determined. Actual carbonate concentration was determined using a multi N/C analyzer. Ferrihydrite samples showed a typical XRD pattern of two-line ferrihydrite, two broad peaks at about 35 and 62° respectively. The BET surfaces (two replicates) were 259.2 ± 3.1 m2/g and 256.0 ± 2.5 m2/g. The Point Zero of Salt Effect (PZSE) was 7.9 ± 0.2 as bibliographically supported for all fresh and thus not rigorously de-carbonated ferrihydrite samples. The KD of the o,oEDDHA/Fe increased from 27.4 ± 0.6 to 304 ± 6 l/kg by decreasing pH from 9.5 and 5.0 when no carbonate was added. Increasing equilibrium carbonate concentrations between 8.6 10-2 and 76 10-2 mM decreased the KD about two-fold at pH 7.5. The KD values from meso-o,oEDDHA/Fe were up to 1000 fold larger than those of rac-o,oEDDHA/Fe at highest carbonate concentration at pH 7.5 and pH dependency suggests that former binds as inner sphere whereas latter binds as outer sphere. Despite the carbonate competition is unlikely to largely affect the net sorption of the chelate in soil, clear differences between meso-o,oEDDHA/Fe and rac-o,oEDDHA/Fe sorption rate on ferrihydrite in presence of carbonate were found.

Remediation of Perfluoroalkyl Contaminated Aquifers Using an In-situ Two-layer Barrier: Laboratory Batch and Column Study

DTIC Science & Technology

2013-04-01

the only possible pathway which is unfortunately less potent. Thus, the perfluorination in PFC renders these compounds essentially inert to those...5.1 EXPERIMENTS ....................................................................................................21 5.1.1 SORPTION ISOTHERMS...19 Figure 13. Sorption isotherm of laccase on granular activated carbon at 25°C. .....................20 Figure 14

Regularities of the sorption of 1,2,3,4-tetrahydroquinoline derivatives under conditions of reversed phase HPLC

NASA Astrophysics Data System (ADS)

Nekrasova, N. A.; Kurbatova, S. V.; Zemtsova, M. N.

2016-12-01

Regularities of the sorption of 1,2,3,4-tetrahydroquinoline derivatives on octadecylsilyl silica gel and porous graphitic carbon from aqueous acetonitrile solutions were investigated. The effect the molecular structure and physicochemical parameters of the sorbates have on their retention characteristics under conditions of reversed phase HPLC are analyzed.

Aqueous suspensions of carbon nanotubes: surface oxidation, colloidal stability and uranium sorption.

PubMed

Schierz, A; Zänker, H

2009-04-01

The objective of this study is to obtain information on the behaviour of carbon nanotubes (CNTs) as potential carriers of pollutants in the case of accidental CNT release to the environment and on the properties of CNTs as a potential adsorbent material in water purification. The effects of acid treatment of CNTs on (i) the surface properties, (ii) the colloidal stability and (iii) heavy metal sorption are investigated, the latter being exemplified by uranium(VI) sorption. There is a pronounced influence of surface treatment on the behaviour of the CNTs in aqueous suspension. Results showed that acid treatment increases the amount of acidic surface groups on the CNTs. Therefore, acid treatment has an increasing effect on the colloidal stability of the CNTs and on their adsorption capacity for U(VI). Another way to stabilise colloids of pristine CNTs in aqueous suspension is the addition of humic acid.

Surface complexation modeling of americium sorption onto volcanic tuff.

PubMed

Ding, M; Kelkar, S; Meijer, A

2014-10-01

Results of a surface complexation model (SCM) for americium sorption on volcanic rocks (devitrified and zeolitic tuff) are presented. The model was developed using PHREEQC and based on laboratory data for americium sorption on quartz. Available data for sorption of americium on quartz as a function of pH in dilute groundwater can be modeled with two surface reactions involving an americium sulfate and an americium carbonate complex. It was assumed in applying the model to volcanic rocks from Yucca Mountain, that the surface properties of volcanic rocks can be represented by a quartz surface. Using groundwaters compositionally representative of Yucca Mountain, americium sorption distribution coefficient (Kd, L/Kg) values were calculated as function of pH. These Kd values are close to the experimentally determined Kd values for americium sorption on volcanic rocks, decreasing with increasing pH in the pH range from 7 to 9. The surface complexation constants, derived in this study, allow prediction of sorption of americium in a natural complex system, taking into account the inherent uncertainty associated with geochemical conditions that occur along transport pathways. Published by Elsevier Ltd.

Sorption of vapors of some organic liquids on soil humic acid and its relation to partitioning of organic compounds in soil organic matter

USGS Publications Warehouse

Chlou, G.T.; Kile, D.E.; Malcolm, R.L.

1988-01-01

Vapor sorption of water, ethanol, benzene, hexane, carbon tetrachloride, 1,1,1-trichloroethane, trichloroethylene, tetrachloroethylene, and 1,2-dibromoethane on (Sanhedron) soil humic acid has been determined at room temperature. Isotherms for all organic liquids are highly linear over a wide range of relative pressure (P/P??), characteristic of the partitioning (dissolution) of the organic compounds in soil humic acid. Polar liquids exhibit markedly greater sorption capacities on soil humic acid than relatively nonpolar liquids, in keeping with the polar nature of the soil humic acid as a partition medium. The limiting sorption (partition) capacities of relatively non-polar liquids are remarkably similar when expressed in terms of volumes per unit weight of soil humic acid. The soil humic acid is found to be about half as effective as soil organic matter in sorption of relatively nonpolar organic compounds. The nearly constant limiting sorption capacity for nonpolar organic liquids with soil humic acid on a volume-to-weight basis and its efficiency in sorption relative to soil organic matter provide a basis for predicting the approximate sorption (partition) coefficients of similar compounds in uptake by soil in aqueous systems.

Properties of Silurian shales from the Barrandian Basin, Czech Republic

NASA Astrophysics Data System (ADS)

Weishauptová, Zuzana; Přibyl, Oldřich; Sýkorová, Ivana

2017-04-01

Although shale gas-bearing deposits have a markedly lower gas content than coal deposits, great attention has recently been paid to shale gas as a new potential source of fossil energy. Shale gas extraction is considered to be quite economical, despite the lower sorption capacity of shales, which is only about 10% of coal sorption capacities The selection of a suitable locality for extracting shale gas requires the sorption capacity of the shale to be determined. The sorption capacity is determined in the laboratory by measuring the amount of methane absorbed in a shale specimen at a pressure and a temperature corresponding to in situ conditions, using high pressure sorption. According to the principles of reversibility of adsorption/desorption, this amount should be roughly related to the amount of gas released by forced degassing. High pressure methane sorption isotherms were measured on seven representative samples of Silurian shales from the Barrandian Basin, Czech Republic. Excess sorption measurements were performed at a temperature of 45oC and at pressures up to 15 MPa on dry samples, using a manometric method. Experimental methane high-pressure isotherms were fitted to a modified Langmuir equation. The maximum measured excess sorption parameter and the Langmuir sorption capacity parameter were used to study the effect of TOC content, organic maturity, inorganic components and porosity on the methane sorption capacity. The studied shale samples with random reflectance of graptolite 0.56 to 1.76% had a very low TOC content and dominant mineral fractions. Illite was the prevailing clay mineral. The sample porosity ranged from 4.6 to 18.8%. In most samples, the micropore volumes were markedly lower than the meso- and macropore volumes. In the Silurian black shales, the occurrence of fractures parallel with the original sedimentary bending was highly significant. A greater proportion of fragments of carbonaceous particles of graptolites and bitumens in the Barrandian Silurian shales had a smooth surface without pores. No relation has been proven between TOC-normalized excess sorption capacities or the TOC-normalized Langmuir sorption capacities and thermal maturation of the shales. The methane sorption capacities of shale samples show a positive correlation with TOC and a positive correlation with the clay content. The highest sorption capacity was observed in shale samples with the highest percentage of micropores, indicating that the micropore volume in the organic matter and clay minerals is a principal factor affecting the sorption capacity of the shale samples.

Sorption of per- and polyfluoroalkyl substances (PFASs) on filter media: implications for phase partitioning studies.

PubMed

Chandramouli, Bharat; Benskin, Jonathan P; Hamilton, M Coreen; Cosgrove, John R

2015-01-01

Per- and polyfluoroalkyl substances (PFASs), including perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS), are ubiquitous in the environment. Investigations into their fate and potential phase-partitioning behavior require separating solid from aqueous phases via filtration. However, sorption of aqueous-phase PFASs on filtration media may lead to underestimation of PFAS concentrations in the aqueous phase. The authors investigated the sorption of perfluoroalkyl carboxylates, perfluoroalkyl sulfonates, perfluoroalkyl phosphonic acids, perfluoroalkyl phosphinic acids (PFPiAs), polyfluoroalkyl phosphate monoesters, polyfluoroalkyl phosphate diesters (diPAPs), fluorotelomer sulfonates, and perfluorooctane sulfonamide on filtration media. The effects of concentration (3 spiking levels), filter media (4 types), matrix (4 matrices), and compound structure on sorption are reported. Glass fiber filtration resulted in the least sorption, whereas polytetrafluoroethylene filters resulted in the most sorption (up to 98%). Analyte concentration had no significant effect. Sorption was generally consistent across matrix types except for samples affected by aqueous film forming foam deployment, which displayed high sorption of PFOS on nylon filters. Sorption usually increased with an increasing number of carbon or fluorine atoms and was most pronounced for PFPiAs and diPAPs (30–75% sorption). Overall, glass fiber filters are more recommended than nylon filters in environmental samples when phase separation is required. Use of filtration media for PFAS must be preceded by matrix-specific testing to account for unpredictable effects. (C)2014 SETAC

SORPTION OF ELEMENTAL MERCURY BY ACTIVATED CARBONS

EPA Science Inventory

The mechanisms and rate of elemental mercury (HgO) capture by activated carbons have been studied using a bench-scale apparatus. Three types of activated carbons, two of which are thermally activated (PC-100 and FGD) and one with elemental sulfur (S) impregnated in it (HGR), were...

Effects of Natural Organic Matter on PCB-Activated Carbon Sorption Kinetics: Implications for Sediment Capping Applications

EPA Science Inventory

In-situ capping of polychlorinated biphenyl (PCB) contaminated sediments with layers of sorbents such as activated carbon has been proposed, but several technical questions remain regarding long-term effectiveness. An activated carbon amended sediment cap was mimicked in laborat...

A facile synthesis of Fe3O4-charcoal composite for the sorption of a hazardous dye from aquatic environment.

PubMed

Ahmed, Md Juned K; Ahmaruzzaman, M

2015-11-01

Herein, we synthesized Fe3O4-charcoal composite using chemical precipitation technique and utilized it for the sorption of methylene blue from aqueous solution. The synthesized composite was characterized by Infra-red spectroscopy, N2 adsorption-desorption isotherm, X-ray diffraction, selected area electron diffraction, transmission electron microscopy, and vibrating sample magnetometer. The composite depicts absorption bands conforming to Fe-O, -OH, CO, and C-O vibrations. The composite was mesoporous in nature with a surface area of 387.30 m(2) g(-1). The observed diffraction planes correspond to face-centered cubic Fe3O4 and disordered graphitic carbon. The spherical Fe3O4 particles (average diameter ∼13.8 nm) were uniformly distributed in the carbon matrix of the charcoal. The saturation and remanent magnetizations demonstrate its potential for magnetic separation and reuse. The composite showed dye sorption capacities of 97.49 mg g(-1) and 90.85 mg g(-1) in batch and fixed-bed system. Pseudo-second order kinetics and Temkin isotherm best represented the sorption data. The sorption process was endothermic, spontaneous, and administered by electrostatic, π-π dispersive interactions, film, and intraparticle diffusion. Microwave irradiations followed by methanol elution regenerated the dye-loaded composite with nearly no loss in sorption capacity. The recovery of energy and potential utilization of bottom ash enhances the prospective of Fe3O4-charcoal composite for industrial applications. Copyright © 2015 Elsevier Ltd. All rights reserved.

Sorption behaviour of perfluoroalkyl substances in soils.

PubMed

Milinovic, Jelena; Lacorte, Silvia; Vidal, Miquel; Rigol, Anna

2015-04-01

The sorption behaviour of three perfluoroalkyl substances (PFASs), perfluorooctane sulfonic acid (PFOS), perfluorooctanoic acid (PFOA) and perfluorobutane sulfonic acid (PFBS), was studied in six soils with contrasting characteristics, especially in the organic carbon content. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions spiked with increasing concentrations of the target PFAS. The sorption reversibility of PFASs was also tested for some of the samples. Liquid chromatography coupled to tandem mass spectrometry was used to quantify the target PFASs in the solutions. Both the Freundlich and linear models were appropriate to describe the sorption behaviour of PFASs in soils, and enabled us to derive solid-liquid distribution coefficients (Kd) for each compound in each soil. Kd values increased from 19 to 295 mL g(-1) for PFOS, from 2.2 to 38 mL g(-1) for PFOA and from 0.4 to 6.8 mL g(-1) for PFBS, and were positively correlated with the organic carbon content of the soil. KOC values obtained from the correlations were 710, 96 and 17 mL g(-1) for PFOS, PFOA and PFBS, respectively. Whereas Kd values decreased in the sequence PFOS>PFOA>PFBS, desorption yields were lower than 13% for PFOS, from 24 to 58% for PFOA, and from 32 to 60% for PFBS. This shows that the physicochemical characteristics of PFASs, basically their hydrophobicity, controlled their sorption behaviour in soils, with PFOS being the most irreversibly sorbed PFAS. Copyright © 2014 Elsevier B.V. All rights reserved.

Sorption of PAHs and PCBs to activated carbon: coal versus biomass-based quality.

PubMed

Amstaetter, Katja; Eek, Espen; Cornelissen, Gerard

2012-04-01

The addition of activated carbon (AC) is an increasingly popular method for pollutant immobilization, and the AC material can be made of biomass or coal/fossil feedstock. The aim of the present study was to investigate whether there are differences between pollutant sorption to biomass and coal-based AC in the presence and absence of sediment. Through N(2) and CO(2) adsorption to probe surface area and pore size it was shown that the biomass-based AC had a stronger dominance of narrow pores in the size range 3.5-15Šthan the anthracite-based material. In the absence of sediment, sorption isotherms for the probe compounds pyrene and PCB-101 showed stronger sorption for the biomass-based AC (logarithmic Freundlich coefficients 8.15 for pyrene; 9.91 for PCB-101) than for the anthracite-based one (logarithmic Freundlich coefficients 7.20 and 9.70, respectively). In the presence of sediment, the opposite trend was observed, with the stronger sorption for anthracite-based AC. Thus, the presence of competing and/or pore-blocking sediment constituents reduces sorption to a larger extent for biomass-derived AC (factor of 5 for pyrene to almost 100 for PCB-101) than for anthracite-based AC (no reduction for pyrene to factor of 5 for PCB-101). This difference is tentatively attributed to the difference in pore size distribution, narrow pores being more prone to clogging, and could have implications for remediation feasibility with AC from different sources. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sorption of nonpolar aromatic contaminants by chlorosilane surface modified natural minerals.

PubMed

Huttenloch, P; Roehl, K E; Czurda, K

2001-11-01

The efficacy of the surface modification of natural diatomite and zeolite material by chlorosilanes is demonstrated. Chlorosilanes used were trimethylchlorosilane (TMSCI), tert-butyldimethylchlorosilane (TBDMSCI), dimethyloctadecylchlorosilane (DMODSCI), and diphenyldichlorosilane (DPDSCI) possessing different headgroups and chemical properties. Silanol groups of the diatomite and zeolite were modified by chemical reaction with the chlorosilanes resulting in a stable covalent attachment of the organosilanes to the mineral surface. The alteration of surface properties of the modified material was proved by measurements of water adsorption capacity, total organic carbon (TOC) content, and thermoanalytical data. The surface modified material showed great stability even when exposed to extremes in ionic strength, pH, and to pure organic solvents. Sorption of toluene, o-xylene, and naphthalene from water was greatly enhanced by the surface modification compared to the untreated materials which showed no measurable sorption of these compounds. The enhanced sorption was dependent on the organic carbon content as well as on chemical characteristics of the chlorosilanes used. Batch sorption experiments showed that the phenyl headgroups of DPDSCI have the best affinity for aromatic compounds. Removal from an aqueous solution of 10 mg/L of naphthalene, o-xylene, and toluene was 71%, 60%, and 30% for surface modified diatomite and 51%, 30%, and 16% for modified clinoptilolite, respectively. Sorption data were well described by the Freundlich isotherm equation, which indicated physical adsorption onto the lipophilic surface rather than partitioning into the surface organic phase. The chlorosilane modified materials have an apparent potential for application in environmental technologies such as permeable reactive barriers (PRB) or wastewater treatment.

Removal of dissolved organic carbon by aquifer material: Correlations between column parameters, sorption isotherms and octanol-water partition coefficient.

PubMed

Pradhan, Snigdhendubala; Boernick, Hilmar; Kumar, Pradeep; Mehrotra, Indu

2016-07-15

The correlation between octanol-water partition coefficient (KOW) and the transport of aqueous samples containing single organic compound is well documented. The concept of the KOW of river water containing the mixture of organics was evolved by Pradhan et al. (2015). The present study aims at determining the KOW and sorption parameters of synthetic aqueous samples and river water to finding out the correlation, if any. The laboratory scale columns packed with aquifer materials were fed with synthetic and river water samples. Under the operating conditions, the compounds in the samples did not separate, and all the samples that contain more than one organic compound yielded a single breakthrough curve. Breakthrough curves simulated from sorption isotherms were compared with those from the column runs. The sorption parameters such as retardation factor (Rf), height of mass transfer zone (HMTZ), rate of mass transfer zone (RMTZ), breakpoint column capacity (qb) and maximum column capacity (qx) estimated from column runs, sorption isotherms and models developed by Yoon-Nelson, Bohart-Adam and Thomas were in agreement. The empirical correlations were found between the KOW and sorption parameters. The transport of the organics measured as dissolved organic carbon (DOC) through the aquifer can be predicted from the KOW of the river water and other water samples. The novelty of the study is to measure KOW and to envisage the fate of the DOC of the river water, particularly during riverbank filtration. Statistical analysis of the results revealed a fair agreement between the observed and computed values. Copyright © 2016 Elsevier Ltd. All rights reserved.

A conversion of CO2-ECBM related lab observations to reservoir requirements

NASA Astrophysics Data System (ADS)

Gensterblum, Yves; Merkel, Alexej; Busch, Andreas; Krooß, Bernhard

2013-04-01

To predict a CBM production profile either during primary or secondary production, aspects like coal permeability and porosity, density, ash and moisture content, initial gas-in-place (GIP) (from canister desorption tests), gas sorption capacity from laboratory isotherms (to obtain gas saturations and desorption pressure), gas diffusivities, coal volumetrics (thickness and areal extent) need to be understood as a minimum requirement. When dealing with CO2-ECBM selective adsorption, counter diffusion in the coal matrix, or coal shrinkage and swelling (from CH4 desorption and CO2 adsorption, respectively) and the influence of moisture need to be investigated in addition to the parameters above. During CO2-ECBM processes, the areal distribution of the CO2 injected is accomplished by flow through the cleat network. When CO2 is entering the coal matrix by a combined sorption/diffusion process it will adsorb to the coal inner surface and at the same time replace part of the CH4. This replacement occurs either by a reduction in the CH4 partial pressure or by a higher selective sorption of CO2 over CH4. Because of a concentration gradient between CH4 in the matrix compared to the cleat system, CH4 diffuses from the coal matrix into the cleat system where, by pressure drawdown towards a production well, it can be produced. In this context this presentation summarizes gas (CO2, CH4) and water sorption on coal and specifically addresses the following topics: • CH4 and CO2 sorption capacity as a function depth and rank • CO2 and CH4 sorption on natural coals and its dependence on coal specific parameters like coal rank, maceral composition or ash content (Busch and Gensterblum, 2011). • Water sorption on coal, its dependence on coal properties such as rank and coal chemistry and gas sorption in the presence of water (Busch and Gensterblum, 2011). • Uncertainties in reservoir characterisation (Gensterblum et al., 2010; Gensterblum et al., 2009) • Sorption uptake kinetic as a function of surface coverage and the influence of moisture on the kinetic Busch, A. and Gensterblum, Y., 2011. CBM and CO2-ECBM related sorption processes in coal: A review. International Journal of Coal Geology, 87: 49-71. Gensterblum, Y. et al., 2010. European inter-laboratory comparison of high pressure CO2 sorption isotherms II: Natural coals. International Journal of Coal Geology, 84(2): 115-124. Gensterblum, Y. et al., 2009. European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon. Carbon, 47(13): 2958-2969.

Enhanced Removal of Lead by Chemically and Biologically Treated Carbonaceous Materials

PubMed Central

Mahmoud, Mohamed E.; Osman, Maher M.; Ahmed, Somia B.; Abdel-Fattah, Tarek M.

2012-01-01

Hybrid sorbents and biosorbents were synthesized via chemical and biological treatment of active carbon by simple and direct redox reaction followed by surface loading of baker's yeast. Surface functionality and morphology of chemically and biologically modified sorbents and biosorbents were studied by Fourier Transform Infrared analysis and scanning electron microscope imaging. Hybrid carbonaceous sorbents and biosorbents were characterized by excellent efficiency and superiority toward lead(II) sorption compared to blank active carbon providing a maximum sorption capacity of lead(II) ion as 500 μmol g−1. Sorption processes of lead(II) by these hybrid materials were investigated under the influence of several controlling parameters such as pH, contact time, mass of sorbent and biosorbent, lead(II) concentration, and foreign ions. Lead(II) sorption mechanisms were found to obey the Langmuir and BET isotherm models. The potential applications of chemically and biologically modified-active carbonaceous materials for removal and extraction of lead from real water matrices were also studied via a double-stage microcolumn technique. The results of this study were found to denote to superior recovery values of lead (95.0–99.0 ± 3.0–5.0%) by various carbonaceous-modified-bakers yeast biosorbents. PMID:22629157

DOE Office of Scientific and Technical Information (OSTI.GOV)

Adib, F.; Bagreev, A.; Bandosz, T.J.

The H{sub 2}S breakthrough capacity was measured on two series of activated carbons of a coconut shell and a bituminous coal origins. To broaden the spectrum of surface features the samples were oxidized using nitric acid or ammonium persulfate under conditions chosen to preserve their pore structures. Then the carbons were characterized using Boehm titration, potentiometric titration, thermal analysis, temperature programmed desorption, sorption of nitrogen, and sorption of water. It was found that the choice of unimpregnated carbon for application as H{sub 2}S adsorbent should be made based on parameters of its acidity such as number of acidic groups, pHmore » of surface, amount of surface groups oxygen, or weight loss associated to decomposition of surface oxygen species. The results obtained from the analyses of six unimpregnated carbon samples suggest that there are certain threshold values of these quantities which, when exceeded, have a dramatic effect on the H{sub 2}S breakthrough capacity.« less

CECOM Index of Technical Papers, International Wire and Cable Symposia,

DTIC Science & Technology

1982-10-18

ROOS. J.SoL. SEVENT4 SYIPOS1U.Mv 1959 8AD-656295) 143 MEAS’JRF1i4T JF THE DEGIEE OF DISPERSION OF CARBON B3LACK IN POYETHY LENE USING A3 SORPTION OF...COMPOSITIONS (AGING, wAXES) BY: YURGENt W.J. PALINCHAK9 So STICKNEY, P.8. TENTH SYMPOSI’UM, 1961 (AD-656172) 218 WATER Ati SORPTION OF ELASTOMERS BY: BIRIGGS9...Fl %R CA3Lf oESIGN AND MANUFAC -3USCHMER G. 55b WATER VAPOR SORPTION OF POI.YETHYLENE: A DECISI -JSCHER, G. 975 CORRELATION BTWCEN LAeORATJRY TESTS

Gas Sorption and Storage Properties of Calixarenes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Patil, Rahul S.; Banerjee, Debasis; Atwood, Jerry L.

2016-12-01

Calixarenes, a class of organic macrocyclic molecules have shown interesting gas sorption properties towards industrially important gases such as carbon di-oxide, hydrogen, methane and acetylene. These macrocycles are involved in weak van der Waals interaction to form multidimensional supramolecular frameworks. The gas-diffusion and subsequent sorption occurs due to a cooperative behavior between neighboring macrocycles. Furthermore, the flexibility at the upper rim functional group also plays a key role in the overall gas uptake of calixarene. In this book chapter, we give a brief account of interaction and diffusion of gases in calixarene and selected derivatives.

Biosorption of nonylphenol by pure algae, field-collected planktons and their fractions.

PubMed

Zhang, Dainan; Ran, Yong; Cao, Xiaoyan; Mao, Jingdong; Cui, Jinfang; Schmidt-Rohr, Klaus

2015-03-01

Algal samples were fractionated into lipid (LP), lipid free (LF), alkaline nonhydrolyzable carbon (ANHC), and acid nonhydrolyzable carbon (NHC) fractions, and were characterized by the quantitative (13)C multiCP NMR technique. The biosorption isotherms for nonylphenol (NP) were established and compared with previously published data for phenanthrene (Phen). The log KOC values are significantly higher for the field-collected plankton samples than for the commercial algae and cultured algae samples, correlating with their lipid contents and aliphatic carbon structure. As the NHC fraction contains more poly(methylene) carbon, it exhibits a higher biosorption capacity. The sorption capacities are negatively related to the polarity index, COO/N-C=O, polar C and O-alkyl C concentrations, but are positively related to the H/O atomic ratios and poly(methylene) carbon. The higher sorption capacities observed for NP than for Phen on the investigated samples are explained by specific interactions such as hydrogen bonding and π-π interaction. Copyright © 2014 Elsevier Ltd. All rights reserved.

The adsorption of gold, palladium and platinum from acidic chloride solutions on mesoporous carbons.

DOE PAGES

Zalupski, Peter R.; McDowell, Rocklan; Dutech, Guy

2014-08-05

Studies on the adsorption characteristics of gold, palladium and platinum on mesoporous carbon (CMK-3) and sulfur-impregnated mesoporous carbon (CMK-3/S) evaluated the benefits/drawbacks of the presence of a layer of elemental sulfur inside mesoporous carbon structures. Adsorption isotherms collected for Au(III), Pd(II) and Pt(IV) on those materials suggest that sulfur does enhance the adsorption of those metal ions in mildly acidic environment (pH 3). The isotherms collected in 1 M HCl show that the benefit of sulfur disappears due to the competing influence of large concentration of hydrogen ions on the ion-exchanging mechanism of metal ions sorption on mesoporous carbon surfaces.more » The collected acid dependencies illustrate similar adsorption characteristics for CMK-3 and CMK-3/S in 1-5 M HCl concentration range. Sorption of metal ions from diluted aqueous acidic mixtures of actual leached electronic waste demonstrated the feasibility of recovery of gold from such liquors.« less

Meta-Analysis of Mass Balances Examining Chemical Fate during Wastewater Treatment

PubMed Central

2008-01-01

Mass balances are an instructive means for investigating the fate of chemicals during wastewater treatment. In addition to the aqueous-phase removal efficiency (Φ), they can inform on chemical partitioning, transformation, and persistence, as well as on the chemical loading to streams and soils receiving, respectively, treated effluent and digested sewage sludge (biosolids). Release rates computed on a per-capita basis can serve to extrapolate findings to a larger scale. This review examines over a dozen mass balances conducted for various organic wastewater contaminants, including prescription drugs, estrogens, fragrances, antimicrobials, and surfactants of differing sorption potential (hydrophobicity), here expressed as the 1-octanol−water partition coefficient (KOW) and the organic carbon normalized sorption coefficient (KOC). Major challenges to mass balances are the collection of representative samples and accurate quantification of chemicals in sludge. A meta-analysis of peer-reviewed data identified sorption potential as the principal determinant governing chemical persistence in biosolids. Occurrence data for organic wastewater compounds detected in digested sludge followed a simple nonlinear model that required only KOW or KOC as the input and yielded a correlation coefficient of 0.9 in both instances. The model predicted persistence in biosolids for the majority (>50%) of the input load of organic wastewater compounds featuring a log10KOW value of greater than 5.2 (log10KOC > 4.4). In contrast, hydrophobicity had no or only limited value for estimating, respectively, Φ and the overall persistence of a chemical during conventional wastewater treatment. PMID:18800497

Sorption of pure N2O to biochars and other organic and inorganic materials under anhydrous conditions

USGS Publications Warehouse

Cornelissen, Gerard; Rutherford, David W.; Arp, Hans Peter H.; Dorsch, Peter; Kelly, Charlene N.; Rostad, Colleen E.

2013-01-01

Suppression of nitrous oxide (N2O) emissions from soil is commonly observed after amendment with biochar. The mechanisms accounting for this suppression are not yet understood. One possible contributing mechanism is N2O sorption to biochar. The sorption of N2O and carbon dioxide (CO2) to four biochars was measured in an anhydrous system with pure N2O. The biochar data were compared to those for two activated carbons and other components potentially present in soils—uncharred pine wood and peat—and five inorganic metal oxides with variable surface areas. Langmuir maximum sorption capacities (Qmax) for N2O on the pine wood biochars (generated between 250 and 500 °C) and activated carbons were 17–73 cm3 g–1 at 20 °C (median 51 cm3 g–1), with Langmuir affinities (b) of 2–5 atm–1 (median 3.4 atm–1). Both Qmaxand b of the charred materials were substantially higher than those for peat, uncharred wood, and metal oxides [Qmax 1–34 cm3 g–1 (median 7 cm3 g–1); b 0.4–1.7 atm–1 (median 0.7 atm–1)]. This indicates that biochar can bind N2O more strongly than both mineral and organic soil materials. Qmax and b for CO2 were comparable to those for N2O. Modeled sorption coefficients obtained with an independent polyparameter—linear free-energy relationship matched measured data within a factor 2 for mineral surfaces but underestimated by a factor of 5–24 for biochar and carbonaceous surfaces. Isosteric enthalpies of sorption of N2O were mostly between −20 and −30 kJ mol–1, slightly more exothermic than enthalpies of condensation (−16.1 kJ mol–1). Qmax of N2O on biochar (50000–130000 μg g–1 biochar at 20 °C) exceeded the N2O emission suppressions observed in the literature (range 0.5–960 μg g–1 biochar; median 16 μg g–1) by several orders of magnitude. Thus, the hypothesis could not be falsified that sorption of N2O to biochar is a mechanism of N2O emission suppression.

Reversible Ammonia Sorption for the Primary Life Support System (PLSS)

NASA Technical Reports Server (NTRS)

Wojtowicz, Marek A.; Cosgrove, Joseph E.; Serio, Michael A.; Jennings, Mallory A.

2012-01-01

Results are presented on the development of regenerable trace-contaminant (TC) sorbent for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). Since ammonia is the most important TC to be captured, data presented in this paper are limited to ammonia sorption, with results relevant to other TCs to be reported at a later time. The currently available TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal. The sorbent is non-regenerable, and its use is associated with appreciable pressure drop, i.e. power consumption. The objective of this work is to demonstrate the feasibility of using vacuum-regenerable sorbents for PLSS application. In this study, several carbon sorbent monoliths were fabricated and tested. Multiple adsorption/vacuum-regeneration cycles were demonstrated at room temperature, as well as carbon surface conditioning that enhances ammonia sorption without impairing sorbent regeneration. Depending on sorbent monolith geometry, the reduction in pressure drop with respect to granular sorbent was found to be between 50% and two orders of magnitude. Resistive heating of the carbon sorbent monolith was demonstrated by applying voltage to the opposite ends of the monolith.

Characterization of Carbon Nano-Onions for Heavy Metal Ion Remediation

EPA Science Inventory

Carbonaceous nanomaterials, such as fullerene C60, carbon nanotubes, and their functionalized derivatives have been demonstrated to possess high sorption capacity for organic and heavy metal contaminants, indicating a potential for remediation application. The actual application ...

Comparison between Soil- and Biochar-Derived Humic Acids: Composition, Conformation, and Phenanthrene Sorption.

PubMed

Jin, Jie; Sun, Ke; Yang, Yan; Wang, Ziying; Han, Lanfang; Wang, Xiangke; Wu, Fengchang; Xing, Baoshan

2018-02-20

Biochar-derived organic matter (BDOM) plays an important role in determining biochar's application potential in soil remediation. However, little is known about the physicochemical properties of BDOM and its sorption of hydrophobic organic compounds (HOCs). Humic acids (HAs) were extracted from oxidized biochars produced from plant straws and animal manures at 450 °C, and their sorption of phenanthrene, a representative of HOCs, was investigated. The organic carbon recovery of biochar-derived HAs (BDHAs) was 13.9-69.3%. The 13 C NMR spectra of BDHAs mainly consisted of aromatic and carboxylic C, while those of soil-derived HAs (SDHAs) contained abundant signals in aliphatic region. BDHAs and SDHAs had comparable CO 2 cumulative surface areas. BDHAs were found to exhibit higher phenanthrene sorption than SDHAs. After the removal of amorphous aromatic components, the logK oc values of BDHAs were significantly decreased, implying that amorphous aromatic C regulated phenanthrene sorption by BDHAs. In contrast, aliphatic moieties dominated phenanthrene sorption by SDHAs, as evidenced by the enhanced sorption after the removal of amorphous aromatics. This study clearly demonstrated the contrasting characteristics and sorption behaviors of BDHA and SDHA, indicating that biochar addition and subsequent weathering could greatly affect native organic matter properties and the fate of HOCs in biochar-amended soils.

Interactions between organic amendments and phosphate fertilizers modify phosphate sorption processes in an acid soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sckefe, C.R.; Patti, A.F.; Clune, T.S.

2008-07-15

To determine how organic amendments and phosphate fertilizers interact to modify P sorption processes, three phosphate fertilizers were applied to lignite- and compost-amended acid soil and incubated for either 3 or 26 days. The fertilizers applied were potassium dihydrogen phosphate, triple superphosphate, and diammonium phosphate (DAP). After 3 days of incubation, sorption of all three P sources was decreased in the lignite-amended treatments, whereas P sorption was increased in the compost-amended treatments. Increased incubation time (26 days) resulted in significantly decreased P sorption when DAP was added to lignite-amended treatments. Addition of triple superphosphate increased P sorption in lignite- andmore » compost-amended treatments and decreased solution pH compared with DAP application. In addition to the effect of P source, differences in P sorption between the lignite- and compost-amended treatments were driven by differences in solution chemistry, predominantly solution pH and cation dynamics. Soil amendment and fertilizer addition also increased microbial activity in the incubation systems, as measured by carbon dioxide respiration. It is proposed that the combination of lignite and DAP may contribute to decreased P sorption in acid soils, with the positive effects likely caused by both chemical and biological processes, including the formation of soluble organic-metal complexes.« less

Phosphorus immobilization in micropores of drinking-water treatment residuals: implications for long-term stability.

PubMed

Makris, Konstantinos C; Harris, Willie G; O'Connor, George A; Obreza, Thomas A

2004-12-15

Drinking-water treatment residuals (WTRs) can immobilize excess soil phosphorus (P), but little is known about the long-term P retention by WTRs. To evaluate the long-term P sorption characteristics of one Fe- and one Al-based WTR, physicochemical properties pertinent to time-dependency and hysteresis of P sorption were assessed. This study also investigated the P sorption mechanisms that could affect the long-term stability of sorbed P by WTRs. Phosphorus sorption kinetics by the WTRs exhibited a slow phase that followed an initial rapid phase, as typically occurs with metal hydroxides. Phosphorus sorption maxima for both Fe- and Al-based WTRs exceeded 9100 mg of P kg(-1) and required a greater specific surface area (SSA) than would be available based on BET-N2 calculations. Electron microprobe analyses of cross-sectional, P-treated particles showed three-dimensional P sorption by WTRs. Carbon dioxide gas sorption was greater than N2, suggesting steric restriction of N2 diffusion by narrow micropore openings. Phosphorus-treated Co2 SSAs were reduced by P treatment, suggesting P sorption by micropores (5-20 A). Mercury intrusion porosimetry indicated negligible macroporosity (pores > 500 A). Slow P sorption kinetics by WTRs may be explained by intraparticle P diffusion in micropores. Micropore-bound P should be stable and immobilized over long periods.

Sorption of fluoroquinolones and sulfonamides in 13 Brazilian soils.

PubMed

Leal, Rafael Marques Pereira; Alleoni, Luis Reynaldo Ferracciú; Tornisielo, Valdemar Luiz; Regitano, Jussara Borges

2013-08-01

Animal production is a leading economic activity in Brazil and antibiotics are widely used. However, the occurrence, behavior, and impacts of antibiotics in Brazilian soils are still poorly known. We evaluated the sorption behavior of four fluoroquinolones (norfloxacin, ciprofloxacin, danofloxacin, and enrofloxacin) and five sulfonamides (sulfadiazine, sulfachloropyridazine, sulfamethoxazole, sulfadimidine, and sulfathiazole) in 13 Brazilian soils with contrasting physical, chemical, and mineralogical properties. Fluoroquinolone sorption was very high (Kd≥544 L kg(-1)) whereas sulfonamide sorption ranged from low to high (Kd=0.7-70.1 L kg(-1)), consistent with previous reports in the literature. Soil texture and cation exchange capacity were the soil attributes that most affected sorption. Cation exchange was the most important sorption mechanism for the fluoroquinolones in highly weathered tropical soils, although cation bridging and ion pairing could not be ruled out. Hydrophobic partition played an important role in the sorption of the sulfonamides, but sorption was also affected by non-hydrophobic interactions with organic and/or mineral surfaces. Sorption for both compound classes tended to be higher in soils with high Al and Fe oxihydroxide contents, but they were not correlated with Kd values. No direct effect of soil pH was seen. The fluoroquinolones are not expected to leach even in worst-case scenarios (soils rich in sand and poor in organic carbon), whereas soil attributes dictate leaching potential for the sulfonamides. Copyright © 2013 Elsevier Ltd. All rights reserved.

Experimental investigation of cephapirin adsorption to quartz filter sands and dune sands

NASA Astrophysics Data System (ADS)

Peterson, Jonathan W.; O'Meara, Theresa A.; Seymour, Michael D.

2008-08-01

Batch experiments were performed to investigate cephapirin (a widely used veterinary antibiotic) adsorption on various size sands of low total organic carbon content (0.08-0.36 wt%). In the aqueous concentration range investigated (11-112 μmol/L cephapirin), adsorption to nearly pure quartz filter sands (0.50-3.35 mm diameter) is low. Isotherms are S-shaped and most display a region of minimum adsorption, where decreased adsorption occurs with increasing solution concentration, followed by increased adsorption at higher concentrations. Cephapirin adsorption to quartz-rich, feldspar-bearing dune sands (0.06-0.35 mm diameter), and the smallest quartz filter sand investigated (0.43-0.50 mm), can be described by linear sorption isotherms over the range of concentrations investigated. Distribution coefficients ( K d) range from 0.94 to 3.45 L/kg. No systematic relationship exists between grain size and amount of adsorption for any of the sands investigated. Cephapirin adsorption is positively correlated to the feldspar ratio (K-feldspar/(albite + Ca-plagioclase). Feldspar-ratio normalization of distribution coefficients was more effective than organic carbon normalization at reducing variability of K d values in the dune sands investigated.

Dependence of samarium-soil interaction on samarium concentration: Implications for environmental risk assessment.

PubMed

Ramírez-Guinart, Oriol; Salaberria, Aitor; Vidal, Miquel; Rigol, Anna

2018-03-01

The sorption and desorption behaviour of samarium (Sm), an emerging contaminant, was examined in soil samples at varying Sm concentrations. The obtained sorption and desorption parameters revealed that soil possessed a high Sm retention capacity (sorption was higher than 99% and desorption lower than 2%) at low Sm concentrations, whereas at high Sm concentrations, the sorption-desorption behaviour varied among the soil samples tested. The fractionation of the Sm sorbed in soils, obtained by sequential extractions, allowed to suggest the soil properties (pH and organic matter solubility) and phases (organic matter, carbonates and clay minerals) governing the Sm-soil interaction. The sorption models constructed in the present work along with the sorption behaviour of Sm explained in terms of soil main characteristics will allow properly assessing the Sm-soil interaction depending on the contamination scenario under study. Moreover, the sorption and desorption K d values of radiosamarium in soils were strongly correlated with those of stable Sm at low concentrations (r = 0.98); indicating that the mobility of Sm radioisotopes and, thus, the risk of radioactive Sm contamination can be predicted using data from low concentrations of stable Sm. Copyright © 2017 Elsevier Ltd. All rights reserved.

Estimation of soil sorption coefficients of veterinary pharmaceuticals from soil properties.

PubMed

ter Laak, Thomas L; Gebbink, Wouter A; Tolls, Johannes

2006-04-01

Environmental exposure assessment of veterinary pharmaceuticals requires estimating the sorption to soil. Soil sorption coefficients of three common, ionizable, antimicrobial agents (oxytetracycline [OTC], tylosin [TYL], and sulfachloropyridazine [SCP]) were studied in relation to the soil properties of 11 different soils. The soil sorption coefficient at natural pH varied from 950 to 7,200, 10 to 370, and 0.4 to 35 L/kg for OTC, TYL, and SCP, respectively. The variation increased by almost two orders of magnitude for OTC and TYL when pH was artificially adjusted. Separate soil properties (pH, organic carbon content, clay content, cation-exchange capacity, aluminum oxyhydroxide content, and iron oxyhydroxide content) were not able to explain more than half the variation observed in soil sorption coefficients. This reflects the complexity of the sorbent-sorbate interactions. Partial-least-squares (PLS) models, integrating all the soil properties listed above, were able to explain as much as 78% of the variation in sorption coefficients. The PLS model was able to predict the sorption coefficient with an accuracy of a factor of six. Considering the pH-dependent speciation, species-specific PLS models were developed. These models were able to predict species-specific sorption coefficients with an accuracy of a factor of three to four. However, the species-specific sorption models did not improve the estimation of sorption coefficients of species mixtures, because these models were developed with a reduced data set at standardized aqueous concentrations. In conclusion, pragmatic approaches like PLS modeling might be suitable to estimate soil sorption for risk assessment purposes.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Parker, Kent E.; Golovich, Elizabeth C.; Wellman, Dawn M.

Iodine sorption onto seven resins and six carbon materials was evaluated using water from well 299-W19-36 on the Hanford Site. These materials were tested using a range of solution-to-solid ratios. The test results are as follows. The efficacy of the resin and granular activated carbon materials was less than predicted based on manufacturers’ performance data. It is hypothesized that this is due to the differences in speciation previously determined for Hanford groundwater. The sorption of iodine is affected by the iodine species in the source water. Iodine loading on resins using source water ranged from 1.47 to 1.70 µg/g withmore » the corresponding K d values from 189.9 to 227.0 mL/g. The sorption values when the iodine is converted to iodide ranged from 2.75 to 5.90 µg/g with the corresponding K d values from 536.3 to 2979.6 mL/g. It is recommended that methods to convert iodine to iodide be investigated in fiscal year (FY) 2015. The chemicals used to convert iodine to iodate adversely affected the sorption of iodine onto the carbon materials. Using as-received source water, loading and K d values ranged from 1.47 to 1.70 µg/g and 189.8 to 226.3 mL/g respectively. After treatment, loading and K d values could not be calculated because there was little change between the initial and final iodine concentration. It is recommended the cause of the decrease in iodine sorption be investigated in FY15. In direct support of CH2M HILL Plateau Remediation Company, Pacific Northwest National Laboratory has evaluated samples from within the 200W pump and treat bioreactors. As part of this analysis, pictures taken within the bioreactor reveal a precipitate that, based on physical properties and known aqueous chemistry, is hypothesized to be iron pyrite or chalcopyrite, which could affect iodine adsorption. It is recommended these materials be tested at different solution-to-solid ratios in FY15 to determine their effect on iodine sorption.« less

The implications of water extractable organic matter (WEOM) on the sorption of typical parent, alkyl and N/O/S-containing polycyclic aromatic hydrocarbons (PAHs) by microplastics.

PubMed

Li, Ruilong; Tan, Huadong; Zhang, Linlin; Wang, Shaopeng; Wang, Yinghui; Yu, Kefu

2018-07-30

Microplastics sorption of persistent organic pollutants (POPs) was the core processes that cause negative effects to biota, and their influencing factors and related mechanisms are poorly understood. In this study, we explored the impacts of water extractable organic matter (WEOM), an important source of endogenous dissolved organic matter in mangrove sediment, on the sorption coefficients of typical parent, alkyl and N/O/S-containing polycyclic aromatic hydrocarbons (PAHs) by microplastics. The presence of L-WEOM (D) impeded the PAHs sorption as the coefficients (K f ) decreased to 10.17 (μg/kg)/(μg/L) n and to 8.39 (μg/kg)/(μg/L) n for fluorene (Flu) and 1-methyl-fluorene (1-M-Flu), respectively. The K f exhibited good linear relationships with the aliphaticity of L-WEOM (p < 0.05) rather than the aromatic carbon/alkyl carbon content (p > 0.05). Under the presences of L-WEOM (D), (S) and (K), the lone pair electrons of N/O/S-containing PAHs was the dominant factor contributing to the obvious difference of the K f values from the other groups. Moreover, the largest impact of L-WEOM (D) on the Flu sorption was in the case of PVC microplastics, while almost no effect was in the case of PS microplastics. The findings of our work may be helpful in improving our understanding of the role of WEOM on the sorption of PAHs to microplastics in the field mangrove sediment. Copyright © 2018 Elsevier Inc. All rights reserved.

Ion reactivity of calcium-deficient hydroxyapatite in standard cell culture media.

PubMed

Gustavsson, J; Ginebra, M P; Engel, E; Planell, J

2011-12-01

Solution-mediated surface reactions occur for most calcium phosphate-based biomaterials and may influence cellular response. A reasonable extrapolation of such processes observed in vitro to in vivo performance requires a deep understanding of the underlying mechanisms. We therefore systematically investigated the nature of ion reactivity of calcium-deficient hydroxyapatite (CDHA) by exposing it for different periods of time to standard cell culture media of different chemical composition (DMEM and McCoy medium, with and without osteogenic supplements and serum proteins). Kinetic ion interaction studies of principal extracellular ions revealed non-linear sorption of Ca²⁺ (∼50% sorption) and K⁺ (∼8%) as well as acidification of all media during initial contact with CDHA (48h). Interestingly, inorganic phosphorus (P(i)) was sorbed from McCoy medium (∼50%) or when using osteogenic media containing β-glycerophosphate, but not from DMEM medium. Non-linear sorption data could be perfectly described by pseudo-first-order and pseudo-second-order sorption models. At longer contact time (21 days), and with frequent renewal of culture medium, sorption of Ca²⁺ remained constant throughout the experiment, while sorption of P(i) gradually decreased in McCoy medium. In great contrast, CDHA began to release P(i) slowly with time when using DMEM medium. Infrared spectra showed that CDHA exposed to culture media had a carbonated surface chemistry, suggesting that carbonate plays a key role in the ion reactivity of CDHA. Our data show that different compositions of the aqueous environment may provoke opposite ion reactivity of CDHA, and this must be carefully considered when evaluating the osteoinductive potential of the material. Copyright © 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Ferrihydrite-impregnated granular activated carbon (FH@GAC) for efficient phosphorus removal from wastewater secondary effluent.

PubMed

Mahardika, Dedy; Park, Hak-Soon; Choo, Kwang-Ho

2018-05-23

Adsorptive removal of phosphorus from wastewater effluents has attracted attention because of its reduced sludge production and potential P recovery. In this study, we investigated granular activated carbons (GACs) impregnated with amorphous ferrihydrite (FH@GAC) for the sorption of phosphorus from aqueous solutions. Preoxidation of intact GAC surfaces using an oxidant (e.g., hypochlorite) and strong acids (e.g., HNO 3 /H 2 SO 4 ) was performed to create active functional groups (e.g., carboxyl or phenolic) for enhanced iron binding, leading to greater phosphorus uptake. Both the rate and the capacity of phosphorus sorption onto FH@GAC had significant, positive relationships (Pearson correlation coefficient r > 0.9) with the product of surface area and Fe content. The pseudo-second-order reaction kinetics explained the P sorption rate better than the pseudo-first-order reaction kinetics, whereas the Langmuir model fit the P sorption isotherm better than the Freundlich model. The iron content in the FH@GAC increased significantly (>10 mg/g) when GAC (e.g., BMC1050) was preoxidized by a 1:1 (w/w) concentrated HNO 3 /H 2 SO 4 mixture. The Langmuir maximum P sorption capacity of a functionalized FH@BMC1050 adsorbent prepared with acid pretreatment was estimated to be substantial (5.73 mg P/g GAC corresponding to 526 mg P/g Fe). This sorption capacity was superior to that of a FH slurry, possibly because the nano-sized FH formed inside the GAC pores (<2.5 nm) can bind phosphate ions more effectively than FH aggregates. Fixed-bed column reactor operation with bicarbonate regeneration showed potential for efficient, continuous phosphorus removal by FH@GAC media. Copyright © 2018 Elsevier Ltd. All rights reserved.

Assessment of spent mushroom substrate as sorbent of fungicides: influence of sorbent and sorbate properties.

PubMed

Marín-Benito, Jesús M; Rodríguez-Cruz, M Sonia; Andrades, M Soledad; Sánchez-Martín, María J

2012-01-01

The capacity of spent mushroom substrate (SMS) as a sorbent of fungicides was evaluated for its possible use in regulating pesticide mobility in the environment. The sorption studies involved four different SMS types in terms of nature and treatment and eight fungicides selected as representative compounds from different chemical groups. Nonlinear sorption isotherms were observed for all SMS-fungicide combinations. The highest sorption was obtained by composted SMS from Agaricus bisporus cultivation. A significant negative and positive correlation was obtained between the K(OC) sorption constants and the polarity index values of sorbents and the K(OW) of fungicides, respectively. The statistic revealed that more than 77% of the variability in the K(OW) could be explained considering these properties jointly. The other properties of both the sorbent (total carbon, dissolved organic carbon, or pH) and the sorbate (water solubility) were nonsignificant. The hysteresis values for cyprodinil (log K(OW)= 4) were for all the sorbents much higher (>3) than for other fungicides. This was consistent with the remaining sorption after desorption considered as an indicator of the sorption efficiency of SMS for fungicides. Changes in the absorption bands of fungicides sorbed by SMS observed by FTIR permitted establishing the interaction mechanism of fungicides with SMS. The findings of this work provide evidence for the potential capacity of SMS as a sorbent of fungicides and the low desorption observed especially for some fungicides, although they suggest that more stabilized or humified organic substrates should be produced to enhance their efficiency in environmental applications. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Effects of sorbents in sorption of agrochemical

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jayasundera, T.; Jayasundera, S.

1996-10-01

Sorption to soil materials is a key process controlling the fate of agrochemicals in the environment. Batch experiments were performed to determine sorption coefficients of metolachlor, alachlor and linuron onto clays, natural organic matter (NOM) coated-clays, and organic sorbents. Our results indicate that the partition coefficient K{sub d} is a function of both sorbent and sorbate properties. The carbon referenced sorption coefficient (K{sub oc}) decreased with increasing polarity of the organic sorbent. Adsorption isotherms onto clays and NOM coated-clays conformed to a Freunlich equation. Studies indicate that at low NOM surface coverage, interactions between NOM and clay surfaces could reducemore » the surface affinity for agrochemical adsorption. Our results suggest that sorption cannot be simply defined as {open_quotes}adsorption{close_quotes} or {open_quotes}partitioning{close_quotes}, but rather there is a continuum of possible interactions. The more polar the solute, the more likely it is that interactions other than hydrophobic will contribute to sorption, causing the currently used K{sub oc}-K{sub ow} correlations to fail.« less

Role of black carbon in the sorption of polychlorinated dibenzo-p-dioxins and dibenzofurans at the Diamond Alkali superfund site, Newark Bay, New Jersey.

PubMed

Lambert, Matthew K; Friedman, Carey; Luey, Pamela; Lohmann, Rainer

2011-05-15

The sorption of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to organic carbon (OC) and black carbon (BC) was measured in two sediment cores taken near the Diamond Alkali superfund site (DA) in the Passaic River and Newark Bay, New Jersey (U.S.A.). An OC partitioning model and a BC-inclusive, Freundlich distribution model were used to interpret measurements of freely dissolved PCDD/Fs using passive samplers in sediment incubations, together with measured sedimentary concentrations of OC, BC, and PCDD/Fs. Samples were also analyzed for polycyclic aromatic hydrocarbons (PAHs) as controls on the two distribution models. The OC partitioning model underpredicted the distribution of PAHs and PCDD/Fs by 10-100-fold. The Freundlich model predicted the distribution of PAHs at the DA to within a factor of 2-3 of observations. Black carbon-water partition coefficients (K(iBC)) for PCDD/Fs, derived from literature results of both field and laboratory studies differed up to 1000-fold from values derived from this study. Contrary to expectations, PCDDs displayed stronger sorption than either PCDFs or PAHs relative to their subcooled liquid aqueous solubilities. Even though the presence of BC in the sediments reduced the overall bioavailability of PCDD/Fs by >90%, the sediments at 2 m depth continue to display the highest pore water activities of PCDD/Fs.

Sorption of halogenated phenols and pharmaceuticals to biochar: affecting factors and mechanisms.

PubMed

Oh, Seok-Young; Seo, Yong-Deuk

2016-01-01

The feasibility of using biochar as a sorbent to remove nine halogenated phenols (2,4-dichlorophenol, 2,4-dibromophenol, 2,4-difluorophenol, 2-chlorophenol, 4-chlorophenol, 2-bromophenol, 4-bromophenol, 2-fluorophenol, and 4-fluorophenol) and two pharmaceuticals (triclosan and ibuprofen) from water was examined through a series of batch experiments. Types of biochar, synthesized using various biomasses including fallen leaves, rice straw, corn stalk, used coffee grounds, and biosolids, were evaluated. Compared to granular activated carbon (GAC), most of the biochar samples did not effectively remove halogenated phenols or pharmaceuticals from water. The increase in pH and deprotonation of phenols in biochar systems may be responsible for its ineffectiveness at this task. When pH was maintained at 4 or 7, the sorption capacity of biochar was markedly increased. Considering maximum sorption capacity and properties of sorbents and sorbates, it appears that the sorption capacity of biochar for halogenated phenols is related to the surface area and carbon content of the biochar and the hydrophobicity of halogenated phenols. In the cases of triclosan and ibuprofen, the sorptive capacities of GAC, graphite, and biochars were also significantly affected by pH, according to the point of zero charge (PZC) of sorbents and deprotonation of the pharmaceuticals. Pyrolysis temperature did not affect the sorption capacity of halogenated phenols or pharmaceuticals. Based on the experimental observations, some biochars are good candidates for removal of halogenated phenols, triclosan, and ibuprofen from water and soil.

Understanding the sorption and biotransformation of organic micropollutants in innovative biological wastewater treatment technologies.

PubMed

Alvarino, T; Suarez, S; Lema, J; Omil, F

2018-02-15

New technologies for wastewater treatment have been developed in the last years based on the combination of biological reactors operating under different redox conditions. Their efficiency in the removal of organic micropollutants (OMPs) has not been clearly assessed yet. This review paper is focussed on understanding the sorption and biotransformation of a selected group of 17 OMPs, including pharmaceuticals, hormones and personal care products, during biological wastewater treatment processes. Apart from considering the role of "classical" operational parameters, new factors such as biomass conformation and particle size, upward velocity applied or the addition of adsorbents have been considered. It has been found that the OMP removal by sorption not only depends on their physico-chemical characteristics and other parameters, such as the biomass conformation and particle size, or some operational conditions also relevant. Membrane biological reactors (MBR), have shown to enhance sorption and biotransformation of some OMPs. The same applies to technologies bases on direct addition of activated carbon in bioreactors. The OMP biotransformation degree and pathway is mainly driven by the redox potential and the primary substrate activity. The combination of different redox potentials in hybrid reactor systems can significantly enhance the overall OMP removal efficiency. Sorption and biotransformation can be synergistically promoted in biological reactors by the addition of activated carbon. The deeper knowledge of the main parameters influencing OMP removal provided by this review will allow optimizing the biological processes in the future. Copyright © 2017 Elsevier B.V. All rights reserved.

Tunable polymeric sorbent materials for fractionation of model naphthenates.

PubMed

Mohamed, Mohamed H; Wilson, Lee D; Headley, John V

2013-04-04

The sorption properties are reported for several examples of single-component carboxylic acids representing naphthenic acids (NAs) with β-cyclodextrin (β-CD) based polyurethane sorbents. Seven single-component examples of NAs were chosen with variable z values, carbon number, and chemical structure as follows: 2-hexyldecanoic acid (z = 0 and C = 16; S1), n-caprylic acid (z = 0 and C = 8; S2), trans-4-pentylcyclohexanecarboxylic acid (z = -2 and C = 12; S3), 4-methylcyclohexanecarboxylic acid (z = -2 and C = 8; S4), dicyclohexylacetic acid (z = -4; C = 14; S5), 4-pentylbicyclo[2.2.2]octane-1-carboxylic acid (z = -4; C = 14; S6), and lithocholic acid (z = -6; C = 24; S7). The copolymer sorbents were synthesized at three relative β-CD:diisocyanate mole ratios (i.e., 1:1, 1:2, and 1:3) using 4,4'-dicyclohexylmethane diisocyanate (CDI) and 4,4'-diphenylmethane diisocyanate (MDI). The sorption properties of the copolymer sorbents were characterized using equilibrium sorption isotherms in aqueous solution at pH 9.00 with electrospray ionization mass spectrometry. The equilibrium fraction of the unbound carboxylate anions was monitored in the aqueous phase. The sorption properties of the copolymer sorbents (i.e., Qm) were obtained from the Sips isotherm model. The Qm values generally decrease as the number of accessible β-CD inclusion sites in the copolymer framework decreases. The chemical structure of the adsorbates played an important role in their relative uptake, as evidenced by the adsorbate lipophilic surface area (LSA) and the involvement of hydrophobic effects. The copolymers exhibit molecular selective sorption of the single-component carboxylates in mixtures which suggests their application as sorbents for fractionation of mixtures of NAs. By comparison, granular activated carbon (GAC) and chitosan sorbents did not exhibit any significant molecular selective sorption relative to the copolymer materials; however, evidence of variable sorption capacity was observed among the sorbents investigated.

Extended sorption partitioning models for pesticide leaching risk assessments: Can we improve upon the koc concept?

PubMed

Jarvis, Nicholas

2016-01-01

Models used to assess leaching of pesticides to groundwater still rely on the sorption koc value, even though its limitations have been known for several decades, especially for soils of low organic carbon content (i.e. subsoils). This is mainly because the general applicability of any improved model approach that is also simple enough to use for regulatory purposes has not been demonstrated. The objective of this study was to test and compare alternative models of sorption that could be useful in pesticide risk assessment and management. To this end, a database containing the results of batch sorption experiments for pesticides was compiled from published studies in the literature, which placed at least as much emphasis on measurements in subsoil horizons as in topsoil. The database includes 785 data entries from 34 different published studies and for 21 different active substances. Overall, the apparent koc value, koc(app), roughly doubled as the soil organic carbon content decreased by a factor of ten. Nevertheless, in nearly half of the individual datasets, a constant koc value proved to be an adequate model. Further analysis showed that significant increases in koc(app) in subsoil were found primarily for the more weakly adsorbing compounds (koc values

Concentration-dependent polyparameter linear free energy relationships to predict organic compound sorption on carbon nanotubes

PubMed Central

Zhao, Qing; Yang, Kun; Li, Wei; Xing, Baoshan

2014-01-01

Adsorption of organic compounds on carbon nanotubes (CNTs), governed by interactions between molecules and CNTs surfaces, is critical for their fate, transport, bioavailability and toxicity in the environment. Here, we report a promising concentration-dependent polyparameter linear free energy relationships (pp-LFERs) model to describe the compound-CNTs interactions and to predict sorption behavior of chemicals on CNTs in a wide range of concentrations (over five orders of magnitude). The developed pp-LFERs are able to capture the dependence of the ki on equilibrium concentration. The pp-LFERs indexes [r, p, a, b, v] representing different interactions are found to have a good relationship with the aqueous equilibrium concentrations of compounds. This modified model can successfully interpret the relative contribution of each interaction at a given concentration and reliably predict sorption of various chemicals on CNTs. This approach is expected to help develop a better environmental fate and risk assessment model. PMID:24463462

Biochar as a sorbent for chlorinated hydrocarbons - sorption and extraction experiments in single and bi-solute systems

NASA Astrophysics Data System (ADS)

Schreiter, Inga J.; Wefer-Roehl, Annette; Graber, Ellen R.; Schüth, Christoph

2017-04-01

Biochar (BC) is increasingly deemed a potential sorbent for contaminants in soil and water remediation, and brownfield restoration. In this study, sorption and extraction experiments were performed to assess the potential of three different BCs to sorb and retain the chlorinated hydrocarbons trichloroethylene (TCE) and tetrachloroethylene (PCE). BCs studied were produced from wood chips, grain husk, and cattle manure at 450 °C. A commercially available activated carbon (AC) served as a reference. The sorption behaviour was studied in batch experiments in single solute and bi-solute systems. Resulting isotherms were fitted to the Freundlich model. To assess the desorption behaviour, a five-step extraction scheme (water at 40°C, water at 80°C, methanol at 50°C, toluene at 50°C, and n-hexane at 50°) was developed, utilizing Accelerated Solvent Extraction. Isotherms revealed distinct differences in sorption behaviour depending on BC feedstock. Sorption capacity ranked as follows: wood chip BC > grain husk BC > cattle manure BC for both contaminants. This sequence could be attributable to an increasing specific surface area, an increasing amount of carbon, and a decreasing ash content of the sorbents. It is noteworthy that all three BCs were more effective in adsorbing TCE, which is surprising, given the higher logKow of PCE. The reverse was observed for the AC. Here, sorption is purely driven by the hydrophobicity of the compound rather than sorbent properties. In bi-solute experiments, PCE sorbed as good as or stronger than TCE, yet the total mass of sorbed compounds increased slightly. In contrast, AC showed a significant decrease of TCE sorption and no significant changes in the total mass sorbed. Extraction experiments revealed that for all BCs a large fraction of the contaminants could not be readily desorbed. In all cases, water remobilized < 5 % of the total contaminant mass and up to 70 % could not be extracted by any of the solvents. The findings suggest that BC is a promising sorbent for mixed contaminant systems as it offers a diverse nature of sorption sites and is more effective in long-term immobilization than AC.

Assessment of agro-industrial and composted organic wastes for reducing the potential leaching of triazine herbicide residues through the soil.

PubMed

Fenoll, José; Vela, Nuria; Navarro, Ginés; Pérez-Lucas, Gabriel; Navarro, Simón

2014-09-15

In this study, we examined the effect of four different organic wastes--composted sheep manure (CSM), spent coffee grounds (SCG), composted pine bark (CPB) and coir (CR)--on the sorption, persistence and mobility of eight symmetrical and two asymmetrical-triazine herbicides: atrazine, propazine, simazine, terbuthylazine (chlorotriazines), prometon (methoxytriazine), prometryn, simetryn, terbutryn (methylthiotriazines), metamitron and metribuzin (triazinones). The downward movement of herbicides was monitored using disturbed soil columns packed with a clay loam soil (Hipercalcic calcisol) under laboratory conditions. For unamended and amended soils, the groundwater ubiquity score (GUS) was calculated for each herbicide on the basis of its persistence (as t½) and mobility (as KOC). All herbicides showed medium/high leachability through the unamended soils. The addition of agro-industrial and composted organic wastes at a rate of 10% (w:w) strongly decreased the mobility of herbicides. Sorption coefficients normalized to the total soil organic carbon (KOC) increased in the amended soils. These results suggest that used organic wastes could be used to enhance the retention and reduce the mobility of the studied herbicides in soil. Copyright © 2014 Elsevier B.V. All rights reserved.

Influence of soil pH on the sorption of ionizable chemicals: modeling advances.

PubMed

Franco, Antonio; Fu, Wenjing; Trapp, Stefan

2009-03-01

The soil-water distribution coefficient of ionizable chemicals (K(d)) depends on the soil acidity, mainly because the pH governs speciation. Using pH-specific K(d) values normalized to organic carbon (K(OC)) from the literature, a method was developed to estimate the K(OC) of monovalent organic acids and bases. The regression considers pH-dependent speciation and species-specific partition coefficients, calculated from the dissociation constant (pK(a)) and the octanol-water partition coefficient of the neutral molecule (log P(n)). Probably because of the lower pH near the organic colloid-water interface, the optimal pH to model dissociation was lower than the bulk soil pH. The knowledge of the soil pH allows calculation of the fractions of neutral and ionic molecules in the system, thus improving the existing regression for acids. The same approach was not successful with bases, for which the impact of pH on the total sorption is contrasting. In fact, the shortcomings of the model assumptions affect the predictive power for acids and for bases differently. We evaluated accuracy and limitations of the regressions for their use in the environmental fate assessment of ionizable chemicals.

A conversion of CO2-ECBM related lab observations to reservoir requirements

NASA Astrophysics Data System (ADS)

Gensterblum, Y.; Merkel, A.; Busch, A.; Krooss, B. M.

2012-04-01

To predict a CBM production profile either during primary or secondary production, aspects like coal permeability and porosity, density, ash and moisture content, initial gas-in-place (GIP) (from canister desorption tests), gas sorption capacity from laboratory isotherms (to obtain gas saturations and desorption pressure), gas diffusivities, coal volumetrics (thickness and areal extent) need to be understood as a minimum requirement. When dealing with CO2-ECBM selective adsorption, counter diffusion in the coal matrix, or coal shrinkage and swelling (from CH4 desorption and CO2 adsorption, respectively) and the influence of moisture need to be investigated in addition to the parameters above. During CO2-ECBM processes, the areal distribution of the CO2 injected is accomplished by flow through the cleat network. When CO2 is entering the coal matrix by a combined sorption/diffusion process it will adsorb to the coal inner surface and at the same time replace part of the CH4. This replacement occurs either by a reduction in the CH4 partial pressure or by a higher selective sorption of CO2 over CH4. Because of a concentration gradient between CH4 in the matrix compared to the cleat system, CH4 diffuses from the coal matrix into the cleat system where, by pressure drawdown towards a production well, it can be produced. In this context this presentation summarizes gas (CO2, CH4) and water sorption on coal and specifically addresses the following topics: • CH4 and CO2 sorption capacity as a function depth and rank • CO2 and CH4 sorption on natural coals and its dependence on coal specific parameters like coal rank, maceral composition or ash content (Busch and Gensterblum, 2011). • Water sorption on coal, its dependence on coal properties such as rank and coal chemistry and gas sorption in the presence of water (Busch and Gensterblum, 2011). • N2, CH4, CO2 displacement experiments and the volumetric response of the coal on the present gas type (sorbing or inert) in the pore system • Uncertainties in reservoir characterisation (Gensterblum et al., 2010; Gensterblum et al., 2009) • Sorption uptake kinetic as a function of surface coverage and the influence of moisture on the kinetic Busch, A. and Gensterblum, Y., 2011. CBM and CO2-ECBM related sorption processes in coal: A review. International Journal of Coal Geology, 87: 49-71. Gensterblum, Y. et al., 2010. European inter-laboratory comparison of high pressure CO2 sorption isotherms II: Natural coals. International Journal of Coal Geology, 84(2): 115-124. Gensterblum, Y. et al., 2009. European inter-laboratory comparison of high pressure CO2 sorption isotherms. I: Activated carbon. Carbon, 47(13): 2958-2969.

Effect of biochar particle size on hydrophobic organic compound sorption kinetics: Applicability of using representative size.

PubMed

Kang, Seju; Jung, Jihyeun; Choe, Jong Kwon; Ok, Yong Sik; Choi, Yongju

2018-04-01

Particle size of biochar may strongly affect the kinetics of hydrophobic organic compound (HOC) sorption. However, challenges exist in characterizing the effect of biochar particle size on the sorption kinetics because of the wide size range of biochar. The present study suggests a novel method to determine a representative value that can be used to show the dependence of HOC sorption kinetics to biochar particle size on the basis of an intra-particle diffusion model. Biochars derived from three different feedstocks are ground and sieved to obtain three daughter products each having different size distributions. Phenanthrene sorption kinetics to the biochars are well described by the intra-particle diffusion model with significantly greater sorption rates observed for finer grained biochars. The time to reach 95% of equilibrium for phenanthrene sorption to biochar is reduced from 4.6-17.9days for the original biochars to <1-4.6days for the powdered biochars with <125μm in size. A moderate linear correlation is found between the inverse square of the representative biochar particle radius obtained using particle size distribution analysis and the apparent phenanthrene sorption rates determined by the sorption kinetics experiments and normalized to account for the variation of the sorption rate-determining factors other than the biochar particle radius. The results suggest that the representative biochar particle radius reasonably describes the dependence of HOC sorption rates on biochar particle size. Copyright © 2017 Elsevier B.V. All rights reserved.

4-MCHM sorption to and desorption from granular activated carbon and raw coal.

PubMed

Jeter, T Scott; Sarver, Emily A; McNair, Harold M; Rezaee, Mohammad

2016-08-01

4-Methylcyclohexanemethanol (4-MCHM) is a saturated higher alicyclic primary alcohol that is used in the froth flotation process for cleaning coal. In early 2014, a large spill of crude chemical (containing primarily 4-MCHM) to the Elk River near Charleston, WV contaminated the local water supply. Carbon filters at the affected water treatment facility quickly became saturated, and the contaminated water was distributed to nearby homes and businesses. Sorption of 4-MCHM to granular activated carbon (GAC) was studied in the laboratory using head space (HS) analysis via gas chromatography with a flame ionization detector (GC-FID). Sorption to raw coal was also investigated, since this material may be of interest as a sorbent in the case of an on-site spill. As expected, sorption to both materials increased with decreased particle size and with increased exposure time; although exposure time proved to be much more important in the case of GAC than for coal. Under similar conditions, GAC sorbed more 4-MCHM than raw coal (e.g., 84.9 vs. 63.1 mg/g, respectively, for 20 × 30 mesh particles exposed to 860 mg/L 4-MCHM solution for 24 h). Desorption from both materials was additionally evaluated. Interestingly, desorption of 4-MCHM on a mass per mass basis was also higher for GAC than for raw coal. Overall, results indicated that GAC readily sorbs 4-MCHM but can also readily release a portion of the chemical, whereas coal sorbs somewhat less 4-MCHM but holds it tightly. Copyright © 2016 Elsevier Ltd. All rights reserved.

Persulfate Oxidation Regeneration of Granular Activated Carbon: Reversible Impacts on Sorption Behavior

EPA Science Inventory

Chemical oxidation regeneration of granular activated carbon (GAC) is a developing technology that can be carried out utilizing thermally-activated persulfate. During chemical regeneration of GAC, aggressive oxidative conditions lead to high acidity (pH < 2) and the accumulation ...

Reactive transport modeling at uranium in situ recovery sites: uncertainties in uranium sorption on iron hydroxides

USGS Publications Warehouse

Johnson, Raymond H.; Tutu, Hlanganani; Brown, Adrian; Figueroa, Linda; Wolkersdorfer, Christian

2013-01-01

Geochemical changes that can occur down gradient from uranium in situ recovery (ISR) sites are important for various stakeholders to understand when evaluating potential effects on surrounding groundwater quality. If down gradient solid-phase material consists of sandstone with iron hydroxide coatings (no pyrite or organic carbon), sorption of uranium on iron hydroxides can control uranium mobility. Using one-dimensional reactive transport models with PHREEQC, two different geochemical databases, and various geochemical parameters, the uncertainties in uranium sorption on iron hydroxides are evaluated, because these oxidized zones create a greater risk for future uranium transport than fully reduced zones where uranium generally precipitates.

Re-evaluation of the sorption behaviour of Bromide and Sulfamethazine under field conditions using leaching data and modelling methods

NASA Astrophysics Data System (ADS)

Gassmann, Matthias; Olsson, Oliver; Höper, Heinrich; Hamscher, Gerd; Kümmerer, Klaus

2016-04-01

The simulation of reactive transport in the aquatic environment is hampered by the ambiguity of environmental fate process conceptualizations for a specific substance in the literature. Concepts are usually identified by experimental studies and inverse modelling under controlled lab conditions in order to reduce environmental uncertainties such as uncertain boundary conditions and input data. However, since environmental conditions affect substance behaviour, a re-evaluation might be necessary under environmental conditions which might, in turn, be affected by uncertainties. Using a combination of experimental data and simulations of the leaching behaviour of the veterinary antibiotic Sulfamethazine (SMZ; synonym: sulfadimidine) and the hydrological tracer Bromide (Br) in a field lysimeter, we re-evaluated the sorption concepts of both substances under uncertain field conditions. Sampling data of a field lysimeter experiment in which both substances were applied twice a year with manure and sampled at the bottom of two lysimeters during three subsequent years was used for model set-up and evaluation. The total amount of leached SMZ and Br were 22 μg and 129 mg, respectively. A reactive transport model was parameterized to the conditions of the two lysimeters filled with monoliths (depth 2 m, area 1 m²) of a sandy soil showing a low pH value under which Bromide is sorptive. We used different sorption concepts such as constant and organic-carbon dependent sorption coefficients and instantaneous and kinetic sorption equilibrium. Combining the sorption concepts resulted in four scenarios per substance with different equations for sorption equilibrium and sorption kinetics. The GLUE (Generalized Likelihood Uncertainty Estimation) method was applied to each scenario using parameter ranges found in experimental and modelling studies. The parameter spaces for each scenario were sampled using a Latin Hypercube method which was refined around local model efficiency maxima. Results of the cumulative SMZ leaching simulations suggest a best conceptualization combination of instantaneous sorption to organic carbon which is consistent with the literature. The best Nash-Sutcliffe efficiency (Neff) was 0.96 and the 5th and 95th percentile of the uncertainty estimation were 18 and 27 μg. In contrast, both scenarios of kinetic Br sorption had similar results (Neff =0.99, uncertainty bounds 110-176 mg and 112-176 mg) but were clearly better than instantaneous sorption scenarios. Therefore, only the concept of sorption kinetics could be identified for Br modelling whereas both tested sorption equilibrium coefficient concepts performed equally well. The reasons for this specific case of equifinality may be uncertainties of model input data under field conditions or an insensitivity of the sorption equilibrium method due to relatively low adsorption of Br. Our results show that it may be possible to identify or at least falsify specific sorption concepts under uncertain field conditions using a long-term leaching experiment and modelling methods. Cases of environmental fate concept equifinality arouse the possibility of future model structure uncertainty analysis using an ensemble of models with different environmental fate concepts.

Sorption of water alkalinity and hardness from high-strength wastewater on bifunctional activated carbon: process optimization, kinetics and equilibrium studies.

PubMed

Amosa, Mutiu K

2016-08-01

Sorption optimization and mechanism of hardness and alkalinity on bifunctional empty fruit bunch-based powdered activation carbon (PAC) were studied. The PAC possessed both high surface area and ion-exchange properties, and it was utilized in the treatment of biotreated palm oil mill effluent. Batch adsorption experiments designed with Design Expert(®) were conducted in correlating the singular and interactive effects of the three adsorption parameters: PAC dosage, agitation speed and contact time. The sorption trends of the two contaminants were sequentially assessed through a full factorial design with three factor interaction models and a central composite design with polynomial models of quadratic order. Analysis of variance revealed the significant factors on each design response with very high R(2) values indicating good agreement between model and experimental values. The optimum operating conditions of the two contaminants differed due to their different regions of operating interests, thus necessitating the utility of desirability factor to get consolidated optimum operation conditions. The equilibrium data for alkalinity and hardness sorption were better represented by the Langmuir isotherm, while the pseudo-second-order kinetic model described the adsorption rates and behavior better. It was concluded that chemisorption contributed majorly to the adsorption process.

Influence of soil biochar aging on sorption of the herbicides MCPA, nicosulfuron, terbuthylazine, indaziflam, and fluoroethyldiaminotriazine.

PubMed

Trigo, Carmen; Spokas, Kurt A; Cox, Lucia; Koskinen, William C

2014-11-12

Sorption of four herbicides and a metabolite of indaziflam on a fresh macadamia nut biochar and biochars aged one or two years in soil was characterized. On fresh biochar, the sorption was terbuthylazine (Kd = 595) > indaziflam (Kd = 162) > MCPA (Kd = 7.5) > fluoroethyldiaminotriazine (Kd = 0.26) and nicosulfuron (Kd = 0). Biochar surface area increased with aging attributed to the loss of a surface film. This was also manifested in a decline in water extractable organic carbon with aging. Correspondingly, an increase in the aromaticity was observed. The higher surface area and porosity in aged biochar increased sorption of indaziflam (KdBC-2yr = 237) and fluoroethyldiaminotriazine (KdBC-1yr = 1.2 and KdBC-2yr = 3.0), but interestingly decreased sorption of terbuthylazine (KdBC-1yr = 312 and KdBC-2yr = 221) and MCPA (KdBC-1yr = 2 and KdBC-2yr = 2). These results will facilitate development of biochars for specific remediation purposes.

Effects of resident water and non-equilibrium adsorption on the primary and enhanced coalbed methane gas recovery

NASA Astrophysics Data System (ADS)

Jahediesfanjani, Hossein

The major part of the gas in coalbed methane and shale gas reservoirs is stored as the adsorbed gas in the coal and organic materials of the black shale internal surfaces. The sorption sites in both reservoirs are composed of several macropores that contain very small pore sizes. Therefore, the adsorption/desorption is very slow process and follows a non-equilibrium trend. The time-dependency of the sorption process is further affected by the reservoir resident water. Water can diffuse into the matrix and adsorption sites, plug the pores and affect the reservoir gas production. This study presents an experimental and theoretical procedure to investigate the effects of the resident water and time-dependency of the sorption process on coalbed and shale gas primary and enhanced recovery by simultaneous CO 2/N2 injection. Series of the experiments are conducted to construct both equilibrium and non-equilibrium single and multi-component isotherms with the presence of water. A novel and rapid data interpretation technique is developed based on the nonequilibrium adsorption/desorption thermodynamics, mass conservation law, and volume filling adsorption theory. The developed technique is implemented to construct both equilibrium and non-equilibrium multi-component multi-phase isotherms from the early time experimental measurements. The non-equilibrium isotherms are incorporated in the coalbed methane/shale gas reservoir simulations to account for the time-dependency of the sorption process. The experimental results indicate that the presence of water in the sorption system reduces both carbon dioxide and nitrogen adsorption rates. Reduction in the adsorption rate for carbon dioxide is more than nitrogen. The results also indicate that the resident water reduces the adsorption ability of low rank coals more than high rank ones. The results of the multi-component sorption tests indicate that increasing the initial mole fraction of the nitrogen gas in the injected CO2/N2 mixture will increase the net carbon dioxide sequestration rate on coals in the presence of water. The optimum CO2/N2 ratio that can result in the maximum carbon dioxide sequestration rate can be obtained by conducting the experiments for various CO2/N2 ratios. The results of applying the developed non-equilibrium interpretation technique for several literature and in-house data indicate that both the equilibrium and non-equilibrium isotherms can be constructed in shorter time period (around 70 times less than the time required with the equilibrium techniques) and with higher accuracy using this method. (Abstract shortened by UMI.)

New Technologies for Dealing with CO2 Emission and Carbonate Discharge Control Issues Associated with Energy Production

NASA Astrophysics Data System (ADS)

Tuwati, Abdulwahab

Carbonates and bicarbonates as two water contaminants and CO2 as an air pollutant are the byproducts of a number of fossil fuel based energy production processes. It is well known that the eco-environmental impacts of the carbon based compounds are rather negative. Discharge of co-produced waters containing carbonates and bicarbonates can lead to the significant increase of alkalinity and sodicity and eventual degradation of the quality of soils. In addition, many studies have indicated that huge CO2 emission into the atmosphere can result in disastrous climate changes in the future. Therefore, people are increasingly interested in controlling these carbon compounds. A number of technologies such as ion exchange and electrodialysis have been developed for removal of carbonates and bicarbonates from co-produced waters. However, they are too expensive to be widely used by energy producers, farmers and ranchers. Although many approaches including membrane filtration have been explored for CO2 emission control, their costs are not acceptable to fossil fuel generating companies at all. Therefore, searching cost-effective methods for control of the carbon compounds have attracted many researchers' attentions. New technologies have been developed in this research to overcome the abovementioned challenges. For example, a regenerable solid sorbent (KTi) synthesized with K2CO3 and nanoporous TiO(OH)2 can be used to capture CO2. The CO2 sorption capacity of KTi is about 36 times higher than that of conventional K2CO3. The highest CO2 sorption capacity achieved with KTi is 1.69 mmol-CO2/g-KTi. It should be noted that the theoretical sorption capacity of the KTi can be as high as 3.32 mmol-CO 2/g-KTi. Therefore, the potential and improvement in CO2 sorption capacity with the use of nanoporous TiO(OH)2 is significant. Moreover, nanostructured KTi based CO2 separation (from flue gas) does not need additional high specific-heat capacity and high vaporization-enthalpy H2O. This creates a favorable condition for considerable decrease in energy consumption of CO2 capture in coal-fired power plants. It is expected that all the technologies developed in this research could significantly benefit energy producers, although many works need to be done before they can be commercialized.

Dependence of pesticide degradation on sorption: nonequilibrium model and application to soil reactors

NASA Astrophysics Data System (ADS)

Guo, Lei; Jury, William A.; Wagenet, Robert J.; Flury, Markus

2000-04-01

The effect of sorption on degradation of the pesticide 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in a soil amended with various amounts of activated carbon (AC). The relationship between sorption and decay of 2,4-D was analyzed using analytical solutions for equilibrium sorption and to a two-site nonequilibrium adsorption model coupled with two first-order degradation terms for the dissolved and sorbed pesticide, respectively. The sorption parameters in the latter model were determined based on data obtained from batch sorption experiments, while those for degradation were obtained from incubation experiments. The adsorption coefficients, ranging from 0.811 to >315 ml g -1, increased at higher AC, and were negatively related to degradation as measured by the first-order rate constant, implying that degradation is faster from the liquid phase than from the sorbed phase. A nonlinear fit of the decay curves to the nonequilibrium model revealed that degradation rate constants were 0.157 and 0.00243 day -1 for the liquid and sorbed phases, respectively, differing by a factor of 65. Similar results were also obtained using the equilibrium model. A parameter sensitivity analysis of the nonequilibrium model indicates that nonequilibrium sorption will initially favor degradation; however, over the long term, will decrease degradation when desorption kinetics becomes the limiting factor in the degradation process. In the presence of a lag phase that allows appreciable amounts of chemical to diffuse into kinetic sorption sites, nonequilibrium sorption will only impede degradation.

Treatment bed microbiological control

NASA Technical Reports Server (NTRS)

Janauer, Gilbert E.; Fitzpatrick, Timothy W.; Kril, Michael B.; Wilber, Georgia A.; Sauer, Richard L.

1987-01-01

The effects of microbial fouling on treatment bed (TB) performance are being studied. Fouling of activated carbon (AC) and ion exchange resins (IEX) by live and devitalized bacteria can cause decreased capacity for selected sorbates with AC and IEX TB. More data are needed on organic species removal in the trace region of solute sorption isotherms. TB colonization was prevented by nonclassical chemical disinfectant compositions (quaternary ammonium resins) applied in suitable configurations. Recently, the protection of carbon beds via direct disinfectant impregnation has shown promise. Effects (of impregnation) upon bed sorption/removal characteristics are to be studied with representative contaminants. The potential need to remove solutes added or produced during water disinfection and/or TB microbiological control must be investigated.

Sorption of imazaquin in soils with positive balance of charges.

PubMed

Rocha, Wadson S D; Regitano, Jussara B; Alleoni, Luis R F; Tornisielo, Valdemar L

2002-10-01

The herbicide imazaquin has both an acid and a basic ionizable groups, and its sorption depends upon the pH, the electric potential (psi0), and the oxide and the organic carbon (OC) contents of the soil. Sorption and extraction experiments using 14C-imazaquin were performed in surface and subsurface samples of two acric oxisols (an anionic "rhodic" acrudox and an anionic "xanthic" acrudox) and one non-acric alfisol (a rhodic kandiudalf), treated at four different pH values. Imazaquin showed low to moderate sorption to the soils. Sorption decreased and aqueous extraction increased as pH increased. Up to pH 5.8, sorption was higher in subsurface than in surface layers of the acric soils, due to the positive balance of charges resulted from the high Fe and Al oxide and the low OC contents. It favored electrostatic interactions with anionic molecules of imazaquin. For the subsurface samples of these highly weathered soils, where psi0 was positive and OC was low, it was not possible to predict sorption just by considering imazaquin speciation and its hydrophobic partition to the organic domains of the soil. Moreover, if Koc measured for thesurface samples were assumed to represent the whole profile in predictive models for leaching potential, then it would result in underestimation of sorption potential in subsurface, and consequently result in overestimation of the leaching potential.

Glyphosate sorption/desorption on biochars - interactions of physical and chemical processes.

PubMed

Hall, Kathleen E; Spokas, Kurt A; Gamiz, Beatriz; Cox, Lucia; Papiernik, Sharon K; Koskinen, William C

2018-05-01

Biochar, a carbon-rich product of biomass pyrolysis, could limit glyphosate transport in soil and remediate contaminated water. The present study investigates the sorption/desorption behavior of glyphosate on biochars prepared from different hardwoods at temperatures ranging from 350 to 900 °C to elucidate fundamental mechanisms. Glyphosate (1 mg L -1 ) sorption on biochars increased with pyrolysis temperature and was highest on 900 °C biochars; however, total sorption was low on a mass basis (<0.1 mg g -1 ). Sorption varied across feedstock materials, and isotherms indicated concentration dependence. Biochars with a greater fraction of micropores exhibited lower sorption capacities, and specific surface groups were also found to be influential. Prepyrolysis treatments with iron and copper, which complex glyphosate in soils, did not alter biochar sorption capacities. Glyphosate did not desorb from biochar with CaCl 2 solution; however, up to 86% of the bound glyphosate was released with a K 2 HPO 4 solution. Results from this study suggest a combined impact of surface chemistry and physical constraints on glyphosate sorption/desorption on biochar. Based on the observed phosphate-induced desorption of glyphosate, the addition of P-fertilizer to biochar-amended soils can remobilize the herbicide and damage non-target plants; therefore, improved understanding of this risk is necessary. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Sorption and transport of acetaminophen, 17alpha-ethynyl estradiol, nalidixic acid with low organic content aquifer sand.

PubMed

Lorphensri, Oranuj; Sabatini, David A; Kibbey, Tohren C G; Osathaphan, Khemarath; Saiwan, Chintana

2007-05-01

The sorption and transport of three pharmaceutical compounds (acetaminophen, an analgesic; nalidixic acid, an antibiotic; and 17alpha-ethynyl estradiol, a synthetic hormone) were examined by batch sorption experiments and solute displacement in columns of silica, alumina, and low organic carbon aquifer sand at neutral pH. Silica and alumina were used to represent negatively-charged and positively-charged fractions of subsurface media. Column transport experiments were also conducted at pH values of 4.3, 6.2, and 8.2 for the ionizable nalidixic acid. The computer program UFBTC was used to fit the breakthrough data under equilibrium and nonequilibrium conditions with linear/nonlinear sorption. Good agreement was observed between the retardation factors derived from column model studies and estimated from equilibrium batch sorption studies. The sorption and transport of nalidixic acid was observed to be highly pH dependent, especially when the pH was near the pK(a) of nalidixic acid (5.95). Thus, near a compound's pK(a) it is especially important that the batch studies be performed at the same pH as the column experiment. While for ionic pharmaceuticals, ion exchange to oppositely-charged surfaces, appears to be the dominant adsorption mechanism, for neutral pharmaceuticals (i.e., acetaminophen, 17alpha-ethynyl estradiol) the sorption correlated well with the K(ow) of the pharmaceuticals, suggesting hydrophobically motivated sorption as the dominant mechanism.

Batch sorption dynamics and equilibrium for the removal of lead ions from aqueous phase using activated carbon developed from coffee residue activated with zinc chloride.

PubMed

Boudrahem, F; Aissani-Benissad, F; Aït-Amar, H

2009-07-01

Lignocellulosic materials are good precursors for the production of activated carbon. In this work, coffee residue has been used as raw material in the preparation of powder activated carbon by the method of chemical activation with zinc chloride for the sorption of Pb(II) from dilute aqueous solutions. The influence of impregnation ratio (ZnCl2/coffee residue) on the physical and chemical properties of the prepared carbons was studied in order to optimize this parameter. The optimum experimental condition for preparing predominantly microporous activated carbons with high pore surface area (890 m2/g) and micropore volume (0.772 cm3/g) is an impregnation ratio of 100%. The developed activated carbon shows substantial capability to sorb lead(II) ions from aqueous solutions and for relative impregnation ratios of 75 and 100%, the maximum uptake is practically the same. Thus, 75% represents the optimal impregnation ratio. Batch experiments were conducted to study the effects of the main parameters such as contact time, initial concentration of Pb(II), solution pH, ionic strength and temperature. The maximum uptake of lead(II) at 25 degrees C was about 63 mg/g of adsorbent at pH 5.8, initial Pb(II) concentration of 10 mg/L, agitation speed of 200 rpm and ionic strength of 0.005 M. The kinetic data were fitted to the models of pseudo-first order and pseudo-second order, and follow closely the pseudo-second order model. Equilibrium sorption isotherms of Pb(II) were analyzed by the Langmuir, Freundlich and Temkin isotherm models. The Freundlich model gives a better fit than the others. Results from this study suggest that activated carbon produced from coffee residue is an effective adsorbent for the removal of lead from aqueous solutions and that ZnCl2 is a suitable activating agent for the preparation of high-porosity carbons.

Sorption of cadmium and lead by clays from municipal incinerator ash- water suspensions

USGS Publications Warehouse

Roy, W.R.; Krapac, I.G.; Steele, J.D.

1993-01-01

The effect of Cl complexation in extracts of a flue gas-scrubber incinerator fly ash sample on the sorption of Cd and Pb by kaolinite and illite was investigated using batch-sorption methods. In the pH range of 5 to 9, Cl complexation may reduce sorption and thus increase the mobility of these metals. When an ash-water suspension was acidified to pH 6.85, the dissolution of Cl and Ca essentially eliminated Cd sorption because of complexation and cationic competition. Cadmium would be considered as either mobile or very mobile under these conditions. Lead was not soluble in the pH- 6.85 suspension. At pH 12, the approximate pH of water in contact with flue gas-scrubber fly ash, Cd was essentially insoluble and Pb occurred as anionic Pb hydroxide. Anionic Pb was sorbed by the two clays, and the extent of sorption was not influenced by Cl or carbonate complexation. Sorption constants, derived from isotherms, suggested that Pb would be relatively immobile in saturated soil-water systems. The recent concern that highly alkaline, flue gas-scrubber fly ash may release environmentally significant concentrations of mobile Pb when placed in an ash-disposal site with a soil liner should be reevaluated in light of this study.

Separation of Carbon Monoxide and Carbon Dioxide for Mars ISRU-Concepts

NASA Technical Reports Server (NTRS)

LeVan, M. Douglas; Finn, John E.; Sridhar, K. R.

2000-01-01

Solid oxide electrolyzers, such as electrolysis cells utilizing yttria-stabilized zirconia, can produce oxygen from Mars atmospheric carbon dioxide and reject carbon monoxide and unreacted carbon dioxide in a separate stream. The oxygen-production process has been shown to be far more efficient if the high-pressure, unreacted carbon dioxide can be separated and recycled back into the feed stream. Additionally, the mass of the adsorption compressor can be reduced. Also, the carbon monoxide by-product is a valuable fuel for space exploration and habitation, with applications from fuel cells to production of hydrocarbons and plastics. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU. Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, respectively. In our research, we will design, construct, and test an innovative, robust, low mass, low power separation device that can recover carbon dioxide and carbon monoxide for Mars ISRU, Such fundamental process technology, involving gas-solid phase separation in a reduced gravitational environment, will help to enable Human Exploration and Development of Space. The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, The separation device will be scaled to operate with a CO2 sorption compressor and a zirconia electrolysis device built at the NASA Ames Research Center and the University of Arizona, Research needs for the design shown are as follows: (1) The best adsorbent for the process must be determined. (2) Adsorption isotherms must be measured, both for pure components and mixtures. (3) Mathematical modeling must be performed to provide a solid framework for design. (4) The separation system must be constructed and tested. (5) System integration must be studied.

Removal of organic compounds from shale gas flowback water.

PubMed

Butkovskyi, Andrii; Faber, Ann-Hélène; Wang, Yue; Grolle, Katja; Hofman-Caris, Roberta; Bruning, Harry; Van Wezel, Annemarie P; Rijnaarts, Huub H M

2018-07-01

Ozonation, sorption to granular activated carbon and aerobic degradation were compared as potential treatment methods for removal of dissolved organic carbon (DOC) fractions and selected organic compounds from shale gas flowback water after pre-treatment in dissolved air flotation unit. Flowback water was characterised by high chemical oxygen demand and DOC. Low molecular weight (LMW) acids and neutral compounds were the most abundant organic fractions, corresponding to 47% and 35% of DOC respectively. Ozonation did not change distribution of organic carbon fractions and concentrations of detected individual organic compounds significantly. Sorption to activated carbon targeted removal of individual organic compounds with molecular weight >115 Da, whereas LMW compounds remained largely unaffected. Aerobic degradation was responsible for removal of LMW compounds and partial ammonium removal, whereas formation of intermediates with molecular weight of 200-350 Da was observed. Combination of aerobic degradation for LMW organics removal with adsorption to activated carbon for removal of non-biodegradable organics is proposed to be implemented between pre-treatment (dissolved air floatation) and desalination (thermal or membrane desalination) steps. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sorption properties of the activated carbon-zeolite composite prepared from coal fly ash for Ni(2+), Cu(2+), Cd(2+) and Pb(2+).

PubMed

Jha, Vinay Kumar; Matsuda, Motohide; Miyake, Michihiro

2008-12-15

Composite materials of activated carbon and zeolite have been prepared successfully by activating coal fly ash (CFA) by fusion with NaOH at 750 degrees C in N(2) followed by hydrothermal treatments under various conditions. Uptake experiments for Ni(2+), Cu(2+), Cd(2+) and Pb(2+) were performed with the materials thus obtained from CFA. Of the various composite materials, that were obtained by hydrothermal treatment with NaOH solution (ca. 4M) at 80 degrees C (a composite of activated carbon and zeolite X/faujasite) proved to be the most suitable for the uptake of toxic metal ions. The relative selectivity of the present sorbents for the various ions was Pb(2+)>Cu(2+)>Cd(2+)>Ni(2+), with equilibrium uptake capacities of 2.65, 1.72, 1.44 and 1.20mmol/g, respectively. The sorption isotherm was a good fit to the Langmuir isotherm and the sorption is thought to progress mainly by ion exchange with Na(+). The overall reaction is pseudo-second order with rate constants of 0.14, 0.17, 0.21 and 0.20Lg/mmol min for the uptake of Pb(2+), Cu(2+), Cd(2+) and Ni(2+), respectively.

Environmental transport of endogenous dairy manure estrogens.

PubMed

Popova, Inna E; Morra, Matthew J

2017-11-02

Although estrogens originating from dairy manure applied to agricultural soils as a fertilizer can potentially contaminate surface water and groundwater, the variables that control transport are poorly understood. Our objective was to assess the potential for off-site movement of endogenous dairy cattle estrogens when manure is applied on fields at agronomically relevant fertilization rates. Estrone (E1), 17α-estradiol (α-E2), and 17β-estradiol (β-E2) were used in laboratory sorption, desorption, and transformation incubations with both manure and an agriculturally relevant soil. Sorption on manure containing 44% organic carbon exceeded sorption on soil containing 0.8% organic carbon by 20 to 150 times, following the pattern of β-E2 > α-E2 > E1. Approximately 20% of E1 and 17% of α-E2 were desorbed from manure, whereas only about 4% of β-E2 was desorbed. Thirty to seventy percent of α-E2 and β-E2 were converted to E1 in soil and manure, making it imperative that transformation reactions be considered when predicting transport and potential biological effects in the environment. Overall results indicate that high organic carbon concentrations and relatively low amounts of desorption inhibit the potential for off-site transport of endogenous dairy manure estrogens.

Complex use of waste in wastewater and circulating water treatment from oil in heat power stations

NASA Astrophysics Data System (ADS)

Nikolaeva, L. A.; Iskhakova, R. Ya.

2017-06-01

Sewage and circulating water from oil of thermal power plants (TPP) generated in fuel-oil shops during washing of electrical equipment and its running into the storm drainage system from the industrial site has been considered in the paper. It has been suggested to use the carbonate sludge of water treatment modified with hydrophobing emulsion as a sorption material for waste and circulating water treatment in thermal power plants. The carbonate sludge is waste accumulated in clarifiers at the stage of natural water pretreatment. General technical characteristics of the sludge, such as moisture, bulk density, total pore volume, ash, etc., have been determined. It has been found that the sludge without additional treatment is a hydrophilic material that has low adsorption capacity and wettability with nonpolar compounds. Therefore, the sludge is treated with organosilicon compounds to reduce the moisture capacity and increase its floatation. Several types of sorption materials based on the carbonate sludge subjected to surface and volume hydrophobization have been developed. During the volume treatment, the hydrophobing compound has been introduced into the material along with the plastifier. In case of the surface treatment, heat-treated granules have been soaked into hydrophobing emulsion. It has been shown that surface hydrophobization is most economically advantageous, because it reduces the consumption of water-repelling agent, wherein the total pore volume and sorption capacity during surface hydrophobization increase by 45 and 25% compared to that during volume hydrophobization. Based on the obtained results, the most effective sorption material has been chosen. To produce this material, it is necessary to sequentially carry out mixing of carbonate sludge with the binder, granulation, calcination, impregnation with a waterrepellent emulsion, and drying of the finished material. The suggested technology to produce the material and use it as a sorbent allows efficient wastewater treatment from oil as well as reduction of anthropogenic pressure on the environment and economic costs of the station for nature protection measures.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clausing, R.E.

Results are summarized for an investigation of the sorption rates of gases on vapor-deposited titanium films. The usefulness of such films for ultrahigh speed vacuum pumping is appraised. The sorption of hydrogen, deuterium, oxygen, nitrogen, carbon monoxide, carbon dioxide, water vapor, helium, argon, and methane onto titanium films was measured for a variety of circumstances using techniques and apparatus developed for this specific purpose. The information obtained and techniques evolved in this study have shown that large-scale getter pumping is feasible and can be a very effective means of pumping many gases. Sticking fractions larger than 0.8 were obtained formore » hydrogen, deuterium, oxygen, nitrogen, carbon monoxide, and carbon dioxide. The experiments have shown that the sticking fraction for gases on vapor-deposited films is a function of the deposition conditions. There is strong evidence to support the supposition that conditions which favor the formation of a porous, fine-grained film structure with a large surface-to-volume ratio produce films with the highest sorption rates. The technique for measuring sticking fractions is new and in many respects unique. It utilizes a very large sorption surface, thus minimizing the perturbing effect of the instrumentation and evaporation apparatus and reducing the hazard of film contamination due to small leaks in the system or outgassing of system components. The method gives especially good accuracy for measurements of sticking fractions approaching unity. The quantity of gas adsorbed, the gas flux onto the getter surface, and the gas flux leaving the getter surface are measured directly. Any two of these three independent measurements can be used to determine the sticking fraction, thereby providing a means of checking the data. The evaporation techniques, substrate surface, and substrate area were chosen to very nearly duplicate the conditions likely to be encountered in the practical application of large-scale getter pumping. (auth)« less

Enhancing oil removal from water by immobilizing multi-wall carbon nanotubes on the surface of polyurethane foam.

PubMed

Keshavarz, Alireza; Zilouei, Hamid; Abdolmaleki, Amir; Asadinezhad, Ahmad

2015-07-01

A surface modification method was carried out to enhance the light crude oil sorption capacity of polyurethane foam (PUF) through immobilization of multi-walled carbon nanotube (MWCNT) on the foam surface at various concentrations. The developed sorbent was characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, thermogravimetric analysis, and tensile elongation test. The results obtained from thermogravimetric and tensile elongation tests showed the improvement of thermal and mechanical resistance of surface-modified foam. The experimental data also revealed that the immobilization of MWCNT on PUF surface enhanced the sorption capacity of light crude oil and reduced water sorption. The highest oil removal capacity was obtained for 1 wt% MWCNT on PUF surface which was 21.44% enhancement in light crude oil sorption compared to the blank PUF. The reusability of surface modified PUF was determined through four cycles of chemical regeneration using petroleum ether. The adsorption of light crude oil with 30 g initial mass showed that 85.45% of the initial oil sorption capacity of this modified sorbent was remained after four regeneration cycles. Equilibrium isotherms for adsorption of oil were analyzed by the Freundlich, Langmuir, Temkin, and Redlich-Peterson models through linear and non-linear regression methods. Results of equilibrium revealed that Langmuir isotherm is the best fitting model and non-linear method is a more accurate way to predict the parameters involved in the isotherms. The overall findings suggested the promising potentials of the developed sorbent in order to be efficiently used in large-scale oil spill cleanup. Copyright © 2015 Elsevier Ltd. All rights reserved.

Thermodynamics of phenanthrene partition into solid organic matter from water.

PubMed

Chen, Bao-liang; Zhu, Li-zhong; Tao, Shu

2005-01-01

The thermodynamic behavior of organic contaminants in soils is essential to develop remediation technologies and assess risk from alternative technologies. Thermodynamics of phenanthrene partition into four solids(three soils and a bentonite) from water were investigated. The thermodynamics parameters (deltaH, deltaG degrees, deltaS degrees) were calculated according to experimental data. The total sorption heats of phenanthrene to solids from water ranged from -7.93 to -17.1 kJ/mol, which were less exothermic than the condensation heat of phenanthrene-solid (i.e., -18.6 kJ/mol). The partition heats of phenanthrene dissolved into solid organic matter ranged from 23.1 to 32.2 kJ/mol, which were less endothermic than the aqueous dissolved heat of phenanthrene (i.e., 40.2 kJ/mol), and were more endothermic than the fusion heat of phenanthrene-solid (i.e., 18.6 kJ/mol). The standard free energy changes, deltaG degrees, are all negative which suggested that phenanthrene sorption into solid was a spontaneous process. The positive values of standard entropy changes, deltaS degrees, show a gain in entropy for the transfer of phenanthrene at the stated standard state. Due to solubility-enhancement of phenanthrene, the partition coefficients normalized by organic carbon contents decrease with increasing system temperature (i.e., ln Koc = -0.284 ln S + 9.82 (n = 4, r2 = 0.992)). The solubility of phenanthrene in solid organic matter increased with increasing temperatures. Transports of phenanthrene in different latitude locations and seasons would be predicted according to its sorption thermodynamics behavior.

Do lab-derived distribution coefficient values of pesticides match distribution coefficient values determined from column and field-scale experiments? A critical analysis of relevant literature.

PubMed

Vereecken, H; Vanderborght, J; Kasteel, R; Spiteller, M; Schäffer, A; Close, M

2011-01-01

In this study, we analyzed sorption parameters for pesticides that were derived from batch and column or batch and field experiments. The batch experiments analyzed in this study were run with the same pesticide and soil as in the column and field experiments. We analyzed the relationship between the pore water velocity of the column and field experiments, solute residence times, and sorption parameters, such as the organic carbon normalized distribution coefficient ( ) and the mass exchange coefficient in kinetic models, as well as the predictability of sorption parameters from basic soil properties. The batch/column analysis included 38 studies with a total of 139 observations. The batch/field analysis included five studies, resulting in a dataset of 24 observations. For the batch/column data, power law relationships between pore water velocity, residence time, and sorption constants were derived. The unexplained variability in these equations was reduced, taking into account the saturation status and the packing status (disturbed-undisturbed) of the soil sample. A new regression equation was derived that allows estimating the values derived from column experiments using organic matter and bulk density with an value of 0.56. Regression analysis of the batch/column data showed that the relationship between batch- and column-derived values depends on the saturation status and packing of the soil column. Analysis of the batch/field data showed that as the batch-derived value becomes larger, field-derived values tend to be lower than the corresponding batch-derived values, and vice versa. The present dataset also showed that the variability in the ratio of batch- to column-derived value increases with increasing pore water velocity, with a maximum value approaching 3.5. American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America.

Enhanced Recyclable Magnetized Palm Shell Waste-Based Powdered Activated Carbon for the Removal of Ibuprofen: Insights for Kinetics and Mechanisms

PubMed Central

Wong, Kien Tiek; Yoon, Yeomin; Jang, Min

2015-01-01

A novel preparation method of magnetized palm shell waste-based powdered activated carbon (MPPAC, avg. size 112 μm) was developed. The prepared MPPAC was assessed by several physicochemical analyses, and batch tests were performed for ibuprofen (IBP) removal. Field emission scanning electron microscopy (FESEM) and N2 gas isotherms revealed that magnetite and maghemite were homogeneous and deposited mostly on the surface of PPAC without a significant clogging effect on the micropores. Isotherm results showed that 3.8% Fe (w/w) impregnated PPAC [MPPAC-Fe(3.8%)] had about 2.2-fold higher maximum sorption capacity (157.3 mg g-1) and a 2.5-fold higher sorption density (0.23 mg m-2) than pristine PPAC. Both Fourier-transform infrared spectroscopy (FTIR) and isotherm data indicated that the high sorption capacity and density of IBP by MPPAC was primarily attributable to donor-acceptor complexes with the C = O group and dispersive π-π interactions with the carbon surface. Based on kinetic and repeated adsorption tests, pore diffusion was the rate-limiting step, and MPPAC-Fe(3.8%) had about 1.9~2.8- and 9.1~15.8-fold higher rate constants than MPPAC-Fe(8.6%) and palm shell-waste granular activated carbon (PGAC, avg. size 621 μm), respectively. MPPAC showed almost eight fold greater re-adsorption capacity than PPAC due to a thermal catalytic effect of magnetite/maghemite. PMID:26496196

Enhanced Recyclable Magnetized Palm Shell Waste-Based Powdered Activated Carbon for the Removal of Ibuprofen: Insights for Kinetics and Mechanisms.

PubMed

Wong, Kien Tiek; Yoon, Yeomin; Jang, Min

2015-01-01

A novel preparation method of magnetized palm shell waste-based powdered activated carbon (MPPAC, avg. size 112 μm) was developed. The prepared MPPAC was assessed by several physicochemical analyses, and batch tests were performed for ibuprofen (IBP) removal. Field emission scanning electron microscopy (FESEM) and N2 gas isotherms revealed that magnetite and maghemite were homogeneous and deposited mostly on the surface of PPAC without a significant clogging effect on the micropores. Isotherm results showed that 3.8% Fe (w/w) impregnated PPAC [MPPAC-Fe(3.8%)] had about 2.2-fold higher maximum sorption capacity (157.3 mg g-1) and a 2.5-fold higher sorption density (0.23 mg m-2) than pristine PPAC. Both Fourier-transform infrared spectroscopy (FTIR) and isotherm data indicated that the high sorption capacity and density of IBP by MPPAC was primarily attributable to donor-acceptor complexes with the C = O group and dispersive π-π interactions with the carbon surface. Based on kinetic and repeated adsorption tests, pore diffusion was the rate-limiting step, and MPPAC-Fe(3.8%) had about 1.9~2.8- and 9.1~15.8-fold higher rate constants than MPPAC-Fe(8.6%) and palm shell-waste granular activated carbon (PGAC, avg. size 621 μm), respectively. MPPAC showed almost eight fold greater re-adsorption capacity than PPAC due to a thermal catalytic effect of magnetite/maghemite.

The potential applications of using compost chars for removing the hydrophobic herbicide atrazine from solution.

PubMed

Tsui, Lo; Roy, William R

2008-09-01

One commercial compost sample was pyrolyzed to produce chars as a sorbent for removing the herbicide atrazine from solution. The sorption behavior of compost-based char was compared with that of an activated carbon derived from corn stillage. When compost was pyrolyzed, the char yield was greater than 45% when heated under air, and 52% when heated under N(2). In contrast, when the corn stillage was pyrolyzed under N(2), the yield was only 22%. The N(2)-BET surface area of corn stillage activated carbon was 439 m(2)/g, which was much greater than the maximum compost char surface area of 72 m(2)/g. However, the sorption affinity of the compost char for dissolved atrazine was comparable to that of the corn stillage activated carbon. This similarity could have resulted from the initial organic waste being subjected to a relatively long period of thermal processes during composting, and thus, the compost was more thermally stable when compared with the raw materials. In addition, microorganisms transformed the organic wastes into amorphous humic substances, and thus, it was likely that the microporisity was enhanced. Although this micropore structure could not be detected by the N(2)-BET method, it was apparent in the atrazine sorption experiment. Overall, the experimental results suggested that the compost sample in current study was a relatively stable material thermally for producing char, and that it has the potential as a feed stock for making high-quality activated carbon.

Measurement of clay surface areas by polyvinylpyrrolidone (PVP) sorption and its use for quantifying illite and smectite abundance

USGS Publications Warehouse

Blum, A.E.; Eberl, D.D.

2004-01-01

A new method has been developed for quantifying smectite abundance by sorbing polyvinylpyrrolidone (PVP) on smectite particles dispersed in aqueous solution. The sorption density of PVP-55K on a wide range of smectites, illites and kaolinites is ~0.99 mg/m2, which corresponds to ~0.72 g of PVP-55K per gram of montmorillonite. Polyvinylpyrrolidone sorption on smectites is independent of layer charge and solution pH. PVP sorption on SiO2, Fe2O3 and ZnO normalized to the BET surface area is similar to the sorption densities on smectites. γ-Al2O3, amorphous Al(OH)3 and gibbsite have no PVP sorption over a wide range of pH, and sorption of PVP by organics is minimal. The insensitivity of PVP sorption densities to mineral layer charge, solution pH and mineral surface charge indicates that PVP sorption is not localized at charged sites, but is controlled by more broadly distributed sorption mechanisms such as Van der Waals’ interactions and/or hydrogen bonding. Smectites have very large surface areas when dispersed as single unit-cell-thick particles (~725 m2/g) and usually dominate the total surface areas of natural samples in which smectites are present. In this case, smectite abundance is directly proportional to PVP sorption. In some cases, however, the accurate quantification of smectite abundance by PVP sorption may require minor corrections for PVP uptake by other phases, principally illite and kaolinite. Quantitative XRD can be combined with PVP uptake measurements to uniquely determine the smectite concentration in such samples.

The structural characterization and H(2) sorption properties of carbon-supported Mg(1-x)Nix nanocrystallites.

PubMed

Bogerd, René; Adelhelm, Philipp; Meeldijk, Johannes H; de Jong, Krijn P; de Jongh, Petra E

2009-05-20

Magnesium (hydride) is a promising system for the reversible on-board storage of hydrogen, but suffers from slow sorption kinetics and a high thermodynamic stability of the hydride. We explored a combined approach to tackle these problems: nanosizing and carbon-supporting the magnesium, and doping it with nickel. Samples were prepared by melt infiltration with magnesium of nanoporous carbon onto which 1-12 wt% nickel nanoparticles had been predeposited. For loadings up to 15 wt% MgH2, 10-30 nm crystallites with different compositions were formed inside the porous carbon, each giving a specific H2 desorption signature. Surprisingly, higher Mg loadings resulted in more homogeneously mixed samples, which was due to the facilitated wetting of the carbon with the magnesium due to the presence of nickel. Hydrogen release temperatures close to that of Mg2NiH4 were observed for high MgH2 loadings (50 wt%) and small amounts of Ni (Mg(0.95)Ni(0.05)). The favourable H2 desorption properties could mainly be attributed to excellent kinetics due to the efficient mixing of magnesium, nickel and carbon on the nanoscale.

The structural characterization and H2 sorption properties of carbon-supported Mg1-xNix nanocrystallites

NASA Astrophysics Data System (ADS)

Bogerd, René; Adelhelm, Philipp; Meeldijk, Johannes H.; de Jong, Krijn P.; de Jongh, Petra E.

2009-05-01

Magnesium (hydride) is a promising system for the reversible on-board storage of hydrogen, but suffers from slow sorption kinetics and a high thermodynamic stability of the hydride. We explored a combined approach to tackle these problems: nanosizing and carbon-supporting the magnesium, and doping it with nickel. Samples were prepared by melt infiltration with magnesium of nanoporous carbon onto which 1-12 wt% nickel nanoparticles had been predeposited. For loadings up to 15 wt% MgH2, 10-30 nm crystallites with different compositions were formed inside the porous carbon, each giving a specific H2 desorption signature. Surprisingly, higher Mg loadings resulted in more homogeneously mixed samples, which was due to the facilitated wetting of the carbon with the magnesium due to the presence of nickel. Hydrogen release temperatures close to that of Mg2NiH4 were observed for high MgH2 loadings (50 wt%) and small amounts of Ni (Mg0.95Ni0.05). The favourable H2 desorption properties could mainly be attributed to excellent kinetics due to the efficient mixing of magnesium, nickel and carbon on the nanoscale.

Sorption of the Rare Earth Elements and Yttrium (REE-Y) in calcite: the mechanism of a new effective tool in identifying paleoearthquakes on carbonate faults

NASA Astrophysics Data System (ADS)

Moraetis, Daniel; Mouslopoulou, Vasiliki; Pratikakis, Alexandros

2015-04-01

A new tool for identifying paleoearthquakes on carbonate faults has been successfully tested on two carbonate faults in southern Europe (the Magnola Fault in Italy and the Spili Fault in Greece): the Rare Earth Element and Yttrium (REE-Y) method (Manighetti et al., 2010; Mouslopoulou et al., 2011). The method is based on the property of the calcite in limestone scarps to absorb the REE and Y from the soil during its residence beneath the ground surface (e.g. before its exhumation due to earthquakes). Although the method is established, the details of the enrichment mechanism are poorly investigated. Here we use published data together with new information from pot-experiments to shed light on the sorption mechanism and the time effectiveness of the REE-Y method. Data from the Magnola and Spili faults show that the average chemical enrichment is ~45%, in REE-Y while the denudation rate of the enriched zones is ~1% higher every 400 years due to exposure of the fault scarp in weathering. They also show that the chemical enrichment is significant even for short periods of residence time (e.g., ~100 years). To better understand the enrichment mechanism, we performed a series of pot experiments, where carbonate tiles extracted from the Spili Fault were buried into soil collected from the hanging-wall of the same fault. We irrigated the pots with artificial rain that equals 5 years of rainfall in Crete and at temperatures of 15oC and 25oC. Following, we performed sorption isotherm, kinetic and pH-edge tests for the europium (Eu), the cerium (Ce) and the ytterbium (Yt) that occur in the calcite minerals. The processes of adsorption and precipitation in the batch experiments are simulated by the Mineql software. The pot experiments indicate incorporation of the REE and Y into the surface of the carbonate tile which is in contact with the soil. The pH of the leached solution during the rain application range from 7.6 to 8.3. Nutrient release like Ca is higher in the leached solution at lower temperature (15oC) probably due to higher calcite solubility (higher dissolved CO2(g) content) and to less adsorption capability of the soil in elevated temperatures. The isotherm sorption modeling showed that REE-(CO3)2 precipitation is the dominant mechanism in the incorporation of REE into calcite, while the kinetic tests showed instant REE sorption (within few hours). Our experiments show that pH>7.5 and temperatures ~25° C favor REE-Y sorption on calcite surface. Hence, due to the REE-Y fast interaction with carbonate scarp face and the low denudation rate due to later weathering, the REE-Y method is considered a reliable method for tracing paleoearthquakes along carbonate fault scarps when the scarp is in contact with soil at temperate climates. The resolution of identifying frequent paleoearthquakes with low residence time in contact with soil is also considered high. References Mouslopoulou, V., Moraetis, D., Fassoulas, C., 2011. Earth Planet. Sci. Lett. 309, 45-55. Manighetti, I., Boucher, E., Chauvel, A., Schlagenhauf, A., Benedetti, L., 2010. Terra Nova 22, 477-482.

Effect of Natural Organic Matter on Plutonium Sorption to Goethite

DOE PAGES

Conroy, Nathan A.; Zavarin, Mavrik; Kersting, Annie B.; ...

2016-11-21

For this research, the effect of citric acid (CA), desferrioxamine B (DFOB), fulvic acid (FA), and humic acid (HA) on plutonium (Pu) sorption to goethite was studied as a function of organic carbon concentration and pH using batch sorption experiments at 5 mg C·L –1 and 50 mg C·L –1 natural organic matter (NOM), 10 –9–10 –10 M 238Pu, and 0.1 g·L –1 goethite concentrations, at pH 3, 5, 7, and 9. Low sorption of ligands coupled with strong Pu complexation decreased Pu sorption at pH 5 and 7, relative to a ligand-free system. Conversely, CA, FA, and HA increasedmore » Pu sorption to goethite at pH 3, suggesting ternary complex formation or, in the case of humic acid, incorporation into HA aggregates. Mechanisms for ternary complex formation were characterized by Fourier transform infrared spectroscopy in the absence of Pu. CA and FA demonstrated clear surface interactions at pH 3, HA appeared unchanged suggesting HA aggregates had formed, and no DFOB interactions were observed. Plutonium sorption decreased in the presence of DFOB (relative to a ligand free system) at all pH values examined. Thus, DFOB does not appear to facilitate formation of ternary Pu-DFOB-goethite complexes. At pH 9, Pu sorption in the presence of all NOM increased relative to pH 5 and 7; speciation models attributed this to Pu(IV) hydrolysis competing with ligand complexation, increasing sorption. In conclusion, the results indicate that in simple Pu-NOM-goethite ternary batch systems, NOM will decrease Pu sorption to goethite at all but particularly low pH conditions.« less

Effect of Natural Organic Matter on Plutonium Sorption to Goethite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Conroy, Nathan A.; Zavarin, Mavrik; Kersting, Annie B.

For this research, the effect of citric acid (CA), desferrioxamine B (DFOB), fulvic acid (FA), and humic acid (HA) on plutonium (Pu) sorption to goethite was studied as a function of organic carbon concentration and pH using batch sorption experiments at 5 mg C·L –1 and 50 mg C·L –1 natural organic matter (NOM), 10 –9–10 –10 M 238Pu, and 0.1 g·L –1 goethite concentrations, at pH 3, 5, 7, and 9. Low sorption of ligands coupled with strong Pu complexation decreased Pu sorption at pH 5 and 7, relative to a ligand-free system. Conversely, CA, FA, and HA increasedmore » Pu sorption to goethite at pH 3, suggesting ternary complex formation or, in the case of humic acid, incorporation into HA aggregates. Mechanisms for ternary complex formation were characterized by Fourier transform infrared spectroscopy in the absence of Pu. CA and FA demonstrated clear surface interactions at pH 3, HA appeared unchanged suggesting HA aggregates had formed, and no DFOB interactions were observed. Plutonium sorption decreased in the presence of DFOB (relative to a ligand free system) at all pH values examined. Thus, DFOB does not appear to facilitate formation of ternary Pu-DFOB-goethite complexes. At pH 9, Pu sorption in the presence of all NOM increased relative to pH 5 and 7; speciation models attributed this to Pu(IV) hydrolysis competing with ligand complexation, increasing sorption. In conclusion, the results indicate that in simple Pu-NOM-goethite ternary batch systems, NOM will decrease Pu sorption to goethite at all but particularly low pH conditions.« less

Sludge-Derived Biochar for Arsenic(III) Immobilization: Effects of Solution Chemistry on Sorption Behavior.

PubMed

Zhang, Weihua; Zheng, Juan; Zheng, Pingping; Tsang, Daniel C W; Qiu, Rongliang

2015-07-01

Recycling sewage sludge by pyrolysis has attracted increasing attention for pollutant removal from wastewater and soils. This study scrutinized As(III) sorption behavior on sludge-derived biochar (SDBC) under different pyrolysis conditions and solution chemistry. The SDBC pyrolyzed at a higher temperature showed a lower As(III) sorption capacity and increasingly nonlinear isotherm due to loss of surface sites and deoxygenation-dehydrogenation. The Langmuir sorption capacity on SDBC (3.08-6.04 mg g) was comparable to other waste-derived sorbents, with the highest As(III) sorption on SDBC pyrolyzed at 400°C for 2 h. The As(III) sorption kinetics best fit with the pseudo-second-order equation, thus suggesting the significance of the availability of surface sites and initial concentration. Sorption of As(III) was faster than that of Cr(VI) but slower than that of Pb(II), which was attributed to their differences in molar volume (correlated to diffusion coefficients) and sorption mechanisms. The X-ray photoelectron spectra revealed an increase of oxide oxygen (O) with a decrease of sorbed water, indicative of ligand exchange with hydroxyl groups on SDBC surfaces. The As(III) sorption was not pH dependent in acidic-neutral range (pH < 8) due to the buffering capacity and surface characteristics of the SDBC; however, sorption was promoted by increasing pH in the alkaline range (pH > 8) because of As(III) speciation in solution. An increasing ionic strength (0.001-0.1 mol L) facilitated As(III) sorption, indicating the predominance of ligand exchange over electrostatic interactions, while high concentrations (0.1 mol L) of competing anions (fluoride, sulfate, carbonate, and phosphate) inhibited As(III) sorption. These results suggest that SDBC is applicable for As(III) immobilization in most environmentally relevant conditions. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Organic Carbon Sorption and Decomposition in Selected Global Soils

DOE Data Explorer

Jagadamma, S.; Mayes, M. A.; Steinweg, J. M.; Wang, G.; Post, W. M.

2014-01-01

This data set reports the results of lab-scale experiments conducted to investigate the dynamics of organic carbon (C) decomposition from several soils from temperate, tropical, arctic, and sub-arctic environments. Results were used to test the newly developed soil microbe decomposition C model--Microbial-ENzyme-medicated Decomposition (MEND).

Catalytic Sorption of (Chloro)Benzene and Napthalene in Aqueous Solutions by Granular Activated Carbon Supported Bimetallic Iron and Palladium Nanoparticles

EPA Science Inventory

Adsorption of benzene, chlorobenzene, and naphthalene on commercially available granular activated carbon (GAC) and bimetallic nanoparticle (Fe/Pd) loaded GAC was investigated for the potential use in active capping of contaminated sediments. Freundlich and Langmuir linearizatio...

INFLUENCE OF SOOT CARBON ON THE BIOACCULUMATION OF SEDIMENT-BOUND POLYCYCLIC AROMATIC HYDROCARBONS BY MARINE BENTHIC INVERTEBRATES: AN INTERSPECIES COMPARISON

EPA Science Inventory

The sorption of polycyclic aromatic hydrocarbons (PAHs) to soot carbon in marine sediments has been hypothesized to reduce PAH bioavailability. This hypothesis was tested for eight species of marine benthic invertebrates (four polychaete worms, Clymenella torquata, Nereis virens,...

Molecular-scale characterization of uranium sorption by bone apatite materials for a permeable reactive barrier demonstration

USGS Publications Warehouse

Fuller, C.C.; Bargar, J.R.; Davis, J.A.

2003-01-01

Uranium binding to bone charcoal and bone meal apatite materials was investigated using U LIII-edge EXAFS spectroscopy and synchrotron source XRD measurements of laboratory batch preparations in the absence and presence of dissolved carbonate. Pelletized bone char apatite recovered from a permeable reactive barrier (PRB) at Fry Canyon, UT, was also studied. EXAFS analyses indicate that U(VI) sorption in the absence of dissolved carbonate occurred by surface complexation of U(VI) for sorbed concentrations ??? 5500 ??g U(VI)/g for all materials with the exception of crushed bone char pellets. Either a split or a disordered equatorial oxygen shell was observed, consistent with complexation of uranyl by the apatite surface. A second shell of atoms at a distance of 2.9 A?? was required to fit the spectra of samples prepared in the presence of dissolved carbonate (4.8 mM total) and is interpreted as formation of ternary carbonate complexes with sorbed U(VI). A U-P distance at 3.5-3.6 A?? was found for most samples under conditions where uranyl phosphate phases did not form, which is consistent with monodentate coordination of uranyl by phosphate groups in the apatite surface. At sorbed concentrations ??? 5500 ??g U(VI)/g in the absence of dissolved carbonate, formation of the uranyl phosphate solid phase, chernikovite, was observed. The presence of dissolved carbonate (4.8 mM total) suppressed the formation of chernikovite, which was not detected even with sorbed U(VI) up to 12 300 ??g U(VI)/g in batch samples of bone meal, bone charcoal, and reagent-grade hydroxyapatite. EXAFS spectra of bone char samples recovered from the Fry Canyon PRB were comparable to laboratory samples in the presence of dissolved carbonate where U(VI) sorption occurred by surface complexation. Our findings demonstrate that uranium uptake by bone apatite will probably occur by surface complexation instead of precipitation of uranyl phosphate phases under the groundwater conditions found at many U-contaminated sites.

Chlorophenol sorption on multi-walled carbon nanotubes: DFT modeling and structure-property relationship analysis.

PubMed

Watkins, Marquita; Sizochenko, Natalia; Moore, Quentarius; Golebiowski, Marek; Leszczynska, Danuta; Leszczynski, Jerzy

2017-02-01

The presence of chlorophenols in drinking water can be hazardous to human health. Understanding the mechanisms of adsorption under specific experimental conditions would be beneficial when developing methods to remove toxic substances from drinking water during water treatment in order to limit human exposure to these contaminants. In this study, we investigated the sorption of chlorophenols on multi-walled carbon nanotubes using a density functional theory (DFT) approach. This was applied to study selected interactions between six solvents, five types of nanotubes, and six chlorophenols. Experimental data were used to construct structure-adsorption relationship (SAR) models that describe the recovery process. Specific interactions between solvents and chlorophenols were taken into account in the calculations by using novel specific mixture descriptors.

Sorption interactions between ethylene glycol and carbon nanotubes

NASA Astrophysics Data System (ADS)

Butyrskaya, E. V.; Belyakova, N. V.; Nechaeva, L. S.; Shaposhnik, V. A.; Selemenev, V. F.

2017-03-01

The adsorption of ethylene glycol by carbon nanoparticles is studied. Carbon nanoparticles with the highest affinity to ethylene glycol are identified, and an adsorption isotherm is constructed. Based on quantum chemical calculations of the energies of interaction between the sorbate and nanotubes with (4,4) and (6,6) chirality, a change in mechanism is revealed upon the monomolecular adsorption of ethylene glycol on carbon nanotubes, and the adsorption isotherm is thus interpreted.

Temperature-dependent sorption of naphthalene, phenanthrene, and pyrene to low organic carbon aquifer sediments

USGS Publications Warehouse

Piatt, Joseph J.; Backhus, Debera A.; Capel, Paul D.; Eisenreich, Steven J.

1996-01-01

Sorption experiments were conducted with naphthalene, phenanthrene, and pyrene on low organic carbon sediments at 4 and 26 °C using batch and column techniques. Experimental controls ensured the absence of biologic and photolytic activity and colloid-free solution supernatants. Equilibrium distribution coefficients (Kd) increased 1.1−1.6 times with a decrease in temperature of 22 °C. Fraction instantaneous sorption (F) values did not change significantly with a decrease in temperature of 22 °C. Desorption rate constants (k2) decreased 1.2−2.6 times with a decrease in temperature of 22 °C. Times to equilibrium were at least 40 h. The magnitude of observed Kd and k2 values and the effect of temperature on Kd (e.g., low enthalpy of sorption) are consistent with sorbate partitioning between the aqueous phase and small amounts of organic matter (foc = 0.02%) on the sediments. The temperature dependence of Kd and k2 may be small as compared to the effects of heterogeneities in field-scale aquifer systems. Thus, thermal gradients may not be of major importance in most saturated subsurface regimes when predicting solute transport. However, aquifer remediation pump-and-treat times could be decreased because increased temperature decreases both retardation and tailing.

Intra-particle migration of mercury in granular polysulfide-rubber-coated activated carbon (PSR-AC)

PubMed Central

Kim, Eun-Ah; Masue-Slowey, Yoko; Fendorf, Scott; Luthy, Richard G.

2011-01-01

The depth profile of mercuric ion after the reaction with polysulfide-rubber-coated activated carbon (PSR-AC) was investigated using micro-x-ray fluorescence (μ-XRF) imaging techniques and mathematical modeling. The μ-XRF results revealed that mercury was concentrated at 0~100 μm from the exterior of the particle after three months of treatment with PSR-AC in 10 ppm HgCl2 aqueous solution. The μ-X-ray absorption near edge spectroscopic (μ-XANES) analyses indicated HgS as a major mercury species, and suggested that the intra-particle mercury transport involved a chemical reaction with PSR polymer. An intra-particle mass transfer model was developed based on either a Langmuir sorption isotherm with liquid phase diffusion (Langmuir model) or a kinetic sorption with surface diffusion (kinetic sorption model). The Langmuir model predicted the general trend of mercury diffusion, although at a slower rate than observed from the μ-XRF map. A kinetic sorption model suggested faster mercury transport, which overestimated the movement of mercuric ions through an exchange reaction between the fast and slow reaction sites. Both μ-XRF and mathematical modeling results suggest mercury removal occurs not only at the outer surface of the PSR-AC particle but also at some interior regions due to a large PSR surface area within an AC particle. PMID:22133913

Extraction of sediment-associated polycyclic aromatic hydrocarbons with granular activated carbon.

PubMed

Rakowska, M I; Kupryianchyk, D; Grotenhuis, T; Rijnaarts, H H M; Koelmans, A A

2013-02-01

Addition of activated carbon (AC) to sediments has been proposed as a method to reduce ecotoxicological risks of sediment-bound contaminants. The present study explores the effectiveness of granular AC (GAC) in extracting polycyclic aromatic hydrocarbon (PAH) from highly contaminated sediments. Four candidate GAC materials were screened in terms of PAH extraction efficiency using single-step 24-h GAC extractions, with traditional 24-h Tenax extraction as a reference. Subsequently, sorption of native PAHs to the best performing GAC 1240W (0.45-1.70 mm) was studied for sediment only and for GAC-sediment mixtures at different GAC-sediment weight ratios, using 76-µm polyoxymethylene (POM) passive samplers. Granular AC sorption parameters for PAHs were determined by subtracting the contribution of PAH sorption to sediment from PAH sorption to the GAC-sediment mixture. It appears that the binding of PAHs and the effectiveness of GAC to reduce sediment porewater concentrations were highly dependent on the GAC-sediment mixing ratio and hydrophobicity of the PAH. Despite the considerable fouling of GAC by organic matter and oil, 50 to 90% of the most available PAH was extracted by the GAC during a 28-d contact time, at a dose as low as 4%, which also is a feasible dose in field-scale applications aimed at cleaning the sediment by GAC addition and removal. Copyright © 2012 SETAC.

Production and characterization of carbonized sorbent products optimized for anionic contaminants

NASA Astrophysics Data System (ADS)

Viglasova, Eva; Fristak, Vladimir; Galambos, Michal; Hood-Nowotny, Rebecca; Soja, Gerhard

2017-04-01

Processing conditions, production methods and feedstock characteristics have been shown to affect the final sorption properties of biochar-based sorbents that have been produced in pyrolysis reactors. The content of O-containing carboxyl, phenolic and hydroxyl functional groups on the biochar surfaces plays a crucial role in sorption chemistry of hazardous materials. The sorption process can be affected by the presence of non-carbonized fractions in biochar matter as well. All these characteristics indicate that biochar shows good potential as a new tool in removal and separation technologies of various pollutants from waste water or contaminated soils. The sorption potential of wood-based biochars for cationic forms of heavy metals has been studied intensively and has already led to successful pilot applications in the field. However, anionic compounds (e.g. phosphate, nitrate, sulphate, As-, Cr-compounds) do not sorb well to unmodified biochar and need specific surface modification of biochar. Based on this fact, we try to obtain data about the sorptive separation of anionic forms of various contaminants from model aqueous solutions by different types of biochar-derived sorbents, or mineral-enriched biochar-derived sorbents. An important part of this research is the assesment of the effects of varying process parameters during biomass carbonisation, the role of biomass feedstock and pre-and/or post-treatment of the biochars onto sorption processes. We specify the most appropriate application strategies with biochar for remediation purposes of waste water or contaminated waters with elevated toxic metal concentrations that might compromise the quality of surface waters. The main aim of research is the preparation of modified biochar sorbent, the characterization of its surface and the investigation about new possibilities of modified biochar sorbent applications for sorption of various contaminants, mainly their anionic forms (e.g. phosphates, nitrates, arsenates). Modification of bamboo-based biochar with clay minerals, the preparation of its composites, could increase the surface area of bamboo-based biochar from 3 to 5 times. Other ways of modification e.g. by using FeCl3 ṡ 6H2O caused a significant increase of sorption ability for anionic forms

Reactive transport modeling of geochemical controls on secondary water quality impacts at a crude oil spill site near Bemidji, MN

USGS Publications Warehouse

Ng, Gene-Hua Crystal.; Bekins, Barbara A.; Cozzarelli, Isabelle M.; Baedecker, Mary Jo; Bennett, Philip C.; Amos, Richard T.; Herkelrath, William N.

2015-01-01

Anaerobic biodegradation of organic amendments and contaminants in aquifers can trigger secondary water quality impacts that impair groundwater resources. Reactive transport models help elucidate how diverse geochemical reactions control the spatiotemporal evolution of these impacts. Using extensive monitoring data from a crude oil spill site near Bemidji, Minnesota (USA), we implemented a comprehensive model that simulates secondary plumes of depleted dissolved O2 and elevated concentrations of Mn2+, Fe2+, CH4, and Ca2+ over a two-dimensional cross section for 30 years following the spill. The model produces observed changes by representing multiple oil constituents and coupled carbonate and hydroxide chemistry. The model includes reactions with carbonates and Fe and Mn mineral phases, outgassing of CH4 and CO2 gas phases, and sorption of Fe, Mn, and H+. Model results demonstrate that most of the carbon loss from the oil (70%) occurs through direct outgassing from the oil source zone, greatly limiting the amount of CH4 cycled down-gradient. The vast majority of reduced Fe is strongly attenuated on sediments, with most (91%) in the sorbed form in the model. Ferrous carbonates constitute a small fraction of the reduced Fe in simulations, but may be important for furthering the reduction of ferric oxides. The combined effect of concomitant redox reactions, sorption, and dissolved CO2 inputs from source-zone degradation successfully reproduced observed pH. The model demonstrates that secondary water quality impacts may depend strongly on organic carbon properties, and impacts may decrease due to sorption and direct outgassing from the source zone.

Dysprosium sorption by polymeric composite bead: robust parametric optimization using Taguchi method.

PubMed

Yadav, Kartikey K; Dasgupta, Kinshuk; Singh, Dhruva K; Varshney, Lalit; Singh, Harvinderpal

2015-03-06

Polyethersulfone-based beads encapsulating di-2-ethylhexyl phosphoric acid have been synthesized and evaluated for the recovery of rare earth values from the aqueous media. Percentage recovery and the sorption behavior of Dy(III) have been investigated under wide range of experimental parameters using these beads. Taguchi method utilizing L-18 orthogonal array has been adopted to identify the most influential process parameters responsible for higher degree of recovery with enhanced sorption of Dy(III) from chloride medium. Analysis of variance indicated that the feed concentration of Dy(III) is the most influential factor for equilibrium sorption capacity, whereas aqueous phase acidity influences the percentage recovery most. The presence of polyvinyl alcohol and multiwalled carbon nanotube modified the internal structure of the composite beads and resulted in uniform distribution of organic extractant inside polymeric matrix. The experiment performed under optimum process conditions as predicted by Taguchi method resulted in enhanced Dy(III) recovery and sorption capacity by polymeric beads with minimum standard deviation. Copyright © 2015 Elsevier B.V. All rights reserved.

H/C atomic ratio as a smart linkage between pyrolytic temperatures, aromatic clusters and sorption properties of biochars derived from diverse precursory materials

PubMed Central

Xiao, Xin; Chen, Zaiming; Chen, Baoliang

2016-01-01

Biochar is increasingly gaining attention due to multifunctional roles in soil amelioration, pollution mitigation and carbon sequestration. It is a significant challenge to compare the reported results from world-wide labs regarding the structure and sorption of biochars derived from various precursors under different pyrolytic conditions due to a lack of a simple linkage. By combining the published works on various biochars, we established a quantitative relationship between H/C atomic ratio and pyrolytic temperature (T), aromatic structure, and sorption properties for naphthalene and phenanthrene. A reverse sigmoid shape between T and the H/C ratio was observed, which was independent of the precursors of biochars, including the ash contents. Linear correlations of Freundlich parameters (N, log Kf) and sorption amount (log Qe, log QA) with H/C ratios were found. A rectangle-like model was proposed to predict the aromatic cluster sizes of biochars from their H/C ratios, and then a good structure-sorption relationship was derived. These quantitative relationships indicate that the H/C atomic ratio is a universal linkage to predict pyrolytic temperatures, aromatic cluster sizes, and sorption characteristics. This study would guide the global study of biochars toward being comparable, and then the development of the structure-sorption relationships will benefit the structural design and environmental application of biochars. PMID:26940984

Sorption-desorption of imidacloprid onto a lacustrine Egyptian soil and its clay and humic acid fractions.

PubMed

Kandil, Mahrous M; El-Aswad, Ahmed F; Koskinen, William C

2015-01-01

Sorption-desorption of the insecticide imidacloprid 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine onto a lacustrine sandy clay loam Egyptian soil and its clay and humic acid (HA) fractions was investigated in 24-h batch equilibrium experiments. Imidacloprid (IMDA) sorption-desorption isotherms onto the three sorbents were found to belong to a non-linear L-type and were best described by the Freundlich model. The value of the IMDA adsorption distribution coefficient, Kd(ads), varied according to its initial concentration and was ranged 40-84 for HA, 14-58 for clay and 1.85-4.15 for bulk soil. Freundlich sorption coefficient, Kf(ads), values were 63.0, 39.7 and 4.0 for HA, clay and bulk soil, respectively. The normalized soil Koc value for imidacloprid sorption was ∼800 indicating its slight mobility in soils. Nonlinear sorption isotherms were indicated by 1/n(ads) values <1 for all sorbents. Values of the hysteresis index (H) were <1, indicating the irreversibility of imidacloprid sorption process with all tested sorbents. Gibbs free energy (ΔG) values indicated a spontaneous and physicosorption process for IMDA and a more favorable sorption to HA than clay and soil. In conclusion, although the humic acid fraction showed the highest capacity and affinity for imidacloprid sorption, the clay fraction contributed to approximately 95% of soil-sorbed insecticide. Clay and humic acid fractions were found to be the major two factors controlling IMDA sorption in soils. The slight mobility of IMDA in soils and the hysteresis phenomenon associated with the irreversibility of its sorption onto, mainly, clay and organic matter of soils make its leachability unlikely to occur.

Sorption characteristics of pesticides on matrix substrates used in biopurification systems.

PubMed

De Wilde, Tineke; Spanoghe, Pieter; Ryckeboer, Jaak; Jaeken, Peter; Springael, Dirk

2009-03-01

On-farm biopurification systems were developed to remove pesticides from contaminated water generated at the farmyard. An important process in the system's efficiency is the sorption of pesticides to the substrates used in the biopurification systems. The composition and type of material present in the biobed are crucial for retention of chemicals. This study investigated the sorption of linuron, isoproturon, metalaxyl, isoxaben, bentazon and lenacil on substrates commonly used in a biopurification system, i.e. cow manure, straw, willow chopping, soil, coconut chips, garden waste compost, and peat mix. Linear, Freundlich, and Langmuir sorption isotherms were fitted to the obtained data. The best fit was obtained with the Freundlich model. More immobile pesticides (i.e. linuron and isoxaben) tended to associate with the organic substrate, while more mobile pesticides partition in the water (i.e. bentazon). According to sorption capacity, the substrates could be classified as peat mix > compost, coco chips, straw > cow manure, willow chopping > sandy loam soil. Sorption capacity was positively correlated with the organic carbon content, CaO and the cation exchange capacity. Furthermore, no significant differences in sorption could be found between technical and formulated isoproturon and bentazon. Moreover, the individual sorption coefficient K(d) was additive, which means that individual sorption coefficients can be used to calculate the sorption coefficients of a mixture of substrates. What concerns the mutual interaction of pesticides it could be observed that the sorption of linuron and metalaxyl was significantly lower in combination with isoproturon and bentazon, while the latter pesticides were not influenced by the presence of linuron and metalaxyl. As guidelines, firstly, it could be stated that using the most sorbing materials such as peat mix, might significantly increase the biopurification systems efficiency. Secondly, the treatment of very mobile pesticides, such as bentazon, should be taken with care as these will easily leach through the system. Additional chemical treatment might be necessary for these type of pesticides.

Pesticide sorption and leaching potential on three Hawaiian soils.

PubMed

Hall, Kathleen E; Ray, Chittaranjan; Ki, Seo Jin; Spokas, Kurt A; Koskinen, William C

2015-08-15

On the Hawaiian Islands, groundwater is the principal source of potable water and contamination of this key resource by pesticides is of great concern. To evaluate the leaching potential of four weak acid herbicides [aminocyclopyrachlor, picloram, metsulfuron-methyl, biologically active diketonitrile degradate of isoxaflutole (DKN)] and two neutral non-ionizable herbicides [oxyfluorfen, alachlor], their sorption coefficients were determined on three prevalent soils from the island of Oahu. Metsulfuron-methyl, aminocylcopyrachlor, picloram, and DKN were relatively low sorbing herbicides (K(oc) = 3-53 mL g(-1)), alachlor was intermediate (K(oc) = 120-150 mL g(-1)), and oxyfluorfen sorbed very strongly to the three soils (K(oc) > 12,000 mL g(-1)). Following determination of K(oc) values, the groundwater ubiquity score (GUS) indices for these compounds were calculated to predicted their behavior with the Comprehensive Leaching Risk Assessment System (CLEARS; Tier-1 methodology for Hawaii). Metsulfuron-methyl, aminocyclopyrachlor, picloram, and DKN would be categorized as likely leachers in all three Hawaiian soils, indicating a high risk of groundwater contamination across the island of Oahu. In contrast, oxyfluorfen, regardless of the degradation rate, would possess a low and acceptable leaching risk due to its high sorption on all three soils. The leaching potential of alachlor was more difficult to classify, with a GUS value between 1.8 and 2.8. In addition, four different biochar amendments to these soils did not significantly alter their sorption capacities for aminocyclopyrachlor, indicating a relatively low impact of black carbon additions from geologic volcanic inputs of black carbon. Due to the fact that pesticide environmental risks are chiefly dependent on local soil characteristics, this work has demonstrated that once soil specific sorption parameters are known one can assess the potential pesticide leaching risks. Published by Elsevier Ltd.

Selective Sorption of Dissolved Organic Carbon Compounds by Temperate Soils

PubMed Central

Jagadamma, Sindhu; Mayes, Melanie A.; Phillips, Jana R.

2012-01-01

Background Physico-chemical sorption onto soil minerals is one of the major processes of dissolved organic carbon (OC) stabilization in deeper soils. The interaction of DOC on soil solids is related to the reactivity of soil minerals, the chemistry of sorbate functional groups, and the stability of sorbate to microbial degradation. This study was conducted to examine the sorption of diverse OC compounds (D-glucose, L-alanine, oxalic acid, salicylic acid, and sinapyl alcohol) on temperate climate soil orders (Mollisols, Ultisols and Alfisols). Methodology Equilibrium batch experiments were conducted using 0–100 mg C L−1 at a solid-solution ratio of 1∶60 for 48 hrs on natural soils and on soils sterilized by γ-irradiation. The maximum sorption capacity, Qmax and binding coefficient, k were calculated by fitting to the Langmuir model. Results Ultisols appeared to sorb more glucose, alanine, and salicylic acid than did Alfisols or Mollisols and the isotherms followed a non-linear pattern (higher k). Sterile experiments revealed that glucose and alanine were both readily degraded and/or incorporated into microbial biomass because the observed Qmax under sterile conditions decreased by 22–46% for glucose and 17–77% for alanine as compared to non-sterile conditions. Mollisols, in contrast, more readily reacted with oxalic acid (Qmax of 886 mg kg−1) and sinapyl alcohol (Qmax of 2031 mg kg−1), and no degradation was observed. The reactivity of Alfisols to DOC was intermediate to that of Ultisols and Mollisols, and degradation followed similar patterns as for Ultisols. Conclusion This study demonstrated that three common temperate soil orders experienced differential sorption and degradation of simple OC compounds, indicating that sorbate chemistry plays a significant role in the sorptive stabilization of DOC. PMID:23209742

Surface complexation model of uranyl sorption on Georgia kaolinite

USGS Publications Warehouse

Payne, T.E.; Davis, J.A.; Lumpkin, G.R.; Chisari, R.; Waite, T.D.

2004-01-01

The adsorption of uranyl on standard Georgia kaolinites (KGa-1 and KGa-1B) was studied as a function of pH (3-10), total U (1 and 10 ??mol/l), and mass loading of clay (4 and 40 g/l). The uptake of uranyl in air-equilibrated systems increased with pH and reached a maximum in the near-neutral pH range. At higher pH values, the sorption decreased due to the presence of aqueous uranyl carbonate complexes. One kaolinite sample was examined after the uranyl uptake experiments by transmission electron microscopy (TEM), using energy dispersive X-ray spectroscopy (EDS) to determine the U content. It was found that uranium was preferentially adsorbed by Ti-rich impurity phases (predominantly anatase), which are present in the kaolinite samples. Uranyl sorption on the Georgia kaolinites was simulated with U sorption reactions on both titanol and aluminol sites, using a simple non-electrostatic surface complexation model (SCM). The relative amounts of U-binding >TiOH and >AlOH sites were estimated from the TEM/EDS results. A ternary uranyl carbonate complex on the titanol site improved the fit to the experimental data in the higher pH range. The final model contained only three optimised log K values, and was able to simulate adsorption data across a wide range of experimental conditions. The >TiOH (anatase) sites appear to play an important role in retaining U at low uranyl concentrations. As kaolinite often contains trace TiO2, its presence may need to be taken into account when modelling the results of sorption experiments with radionuclides or trace metals on kaolinite. ?? 2004 Elsevier B.V. All rights reserved.

Role of soil organic carbon and colloids in sorption and transport of TNT, RDX and HMX in training range soils.

PubMed

Sharma, Prasesh; Mayes, Melanie A; Tang, Guoping

2013-08-01

Contamination of soils and groundwater by munitions compounds (MCs) is of significant concern at many U.S. Department of Defense sites. Soils were collected from operational training ranges in Maryland (APG), Massachusetts (MMR-B and MMR-E) and Washington (JBLM) and sorption and transport studies were conducted to investigate the effects of soil organic carbon (OC) and textural clay content on fate of dissolved MCs (TNT, RDX, HMX). Sorption experiments showed higher distribution coefficients [TNT:42-68 L kg(-1), RDX:6.9-8.7 L kg(-1) and HMX:2.6-3.1 L kg(-1)] in OC rich soils (JBLM, MMR-E) compared to clay rich soils (MMR-B and APG) [TNT:19-21 L kg(-1), RDX:2.5-3.4 L kg(-1), HMX:0.9-1.2 L kg(-1)]. In column experiments, breakthrough of MCs was faster in MMR-B and APG compared to MMR-E and JBLM soils. Among TNT, RDX and HMX, breakthrough was fastest for RDX followed by HMX and TNT for all columns. Defining the colloidal fraction as the difference between unfiltered samples and samples filtered with a 3 kDa filter, ~36%, ~15% and ~9% of TNT, RDX and HMX were found in the colloidal fraction in the solutions from sorption experiments, and around 20% of TNT in the effluent from the transport experiments. Results demonstrate that OC rich soils may enhance sorption and delay transport of TNT, RDX and HMX compared to clay-rich soils. Further, transport of TNT may be associated with soil colloid mobilization. Copyright © 2013 Elsevier Ltd. All rights reserved.

Influence of heteroaggregation processes between intrinsic colloids and carrier colloids on cerium(III) mobility through fractured carbonate rocks.

PubMed

Tran, Emily; Klein Ben-David, Ofra; Teutch, Nadya; Weisbrod, Noam

2016-09-01

Colloid facilitated transport of radionuclides has been implicated as a major transport vector for leaked nuclear waste in the subsurface. Sorption of radionuclides onto mobile carrier colloids such as bentonite and humic acid often accelerates their transport through saturated rock fractures. Here, we employ column studies to investigate the impact of intrinsic, bentonite and humic acid colloids on the transport and recovery of Ce(III) through a fractured chalk core. Ce(III) recovery where either bentonite or humic colloids were added was 7.7-26.9% Ce for all experiments. Greater Ce(III) recovery was observed when both types of carrier colloids were present (25.4-37.4%). When only bentonite colloids were present, Ce(III) appeared to be fractionated between chemical sorption to the bentonite colloid surfaces and heteroaggregation of bentonite colloids with intrinsic carbonate colloids, precipitated naturally in solution. However, scanning electron microscope (SEM) images and colloid stability experiments reveal that in suspensions of humic acid colloids, colloid-facilitated Ce(III) migration results only from the latter attachment mechanism rather than from chemical sorption. This observed heteroaggregation of different colloid types may be an important factor to consider when predicting potential mobility of leaked radionuclides from geological repositories for spent fuel located in carbonate rocks. Copyright © 2016 Elsevier Ltd. All rights reserved.

Compositions and sorptive properties of crop residue-derived chars

USGS Publications Warehouse

Chun, Y.; Sheng, G.; Chiou, G.T.; Xing, B.

2004-01-01

Chars originating from the burning or pyrolysis of vegetation may significantly sorb neutral organic contaminants (NOCs). To evaluate the relationship between the char composition and NOC sorption, a series of char samples were generated by pyrolyzing a wheat residue (Triticum aestivum L) for 6 h at temperatures between 300 ??C and 700 ??C and analyzed for their elemental compositions, surface areas, and surface functional groups. The samples were then studied for their abilities to sorb benzene and nitrobenzene from water. A commercial activated carbon was used as a reference carbonaceous sample. The char samples produced at high pyrolytic temperatures (500-700 ??C) were well carbonized and exhibited a relatively high surface area (>300 m2/g), little organic matter (20% oxygen). The char samples exhibited a significant range of surface acidity/basicity because of their different surface polar-group contents, as characterized by the Boehm titration data and the NMR and FTIR spectra. The NOC sorption by high-temperature chars occurred almost exclusively by surface adsorption on carbonized surfaces, whereas the sorption by low-temperature chars resulted from the surface adsorption and the concurrent smaller partition into the residual organic-matter phase. The chars appeared to have a higher surface affinity for a polar solute (nitrobenzene) than for a nonpolar solute (benzene), the difference being related to the surface acidity/basicity of the char samples.

Preloading hydrous ferric oxide into granular activated carbon for arsenic removal.

PubMed

Jang, Min; Chen, Weifang; Cannon, Fred S

2008-05-01

Arsenic is of concern in water treatment because of its health effects. This research focused on incorporating hydrous ferric oxide (HFO) into granular activated carbon (GAC) for the purpose of arsenic removal. Iron was incorporated into GAC via incipient wetness impregnation and cured at temperatures ranging from 60 to 90 degrees C. X-ray diffractions and arsenic sorption as a function of pH were conducted to investigate the effect of temperature on final iron oxide (hydroxide) and their arsenic removal capabilities. Results revealed that when curing at 60 degrees C, the procedure successfully created HFO in the pores of GAC, whereas at temperatures of 80 and 90 degrees C, the impregnated iron oxide manifested a more crystalline form. In the column tests using synthetic water, the HFO-loaded GAC prepared at 60 degrees C also showed higher sorption capacities than media cured at higher temperatures. These results indicated that the adsorption capacity for arsenic was closely related to the form of iron (hydr)oxide for a given iron content For the column test using a natural groundwater, HFO-loaded GAC (Fe, 11.7%) showed an arsenic sorption capacity of 26 mg As/g when the influent contained 300 microg/L As. Thus, the preloading of HFO into a stable GAC media offered the opportunity to employ fixed carbon bed reactors in water treatment plants or point-of-use filters for arsenic removal.

Compound-Specific Stable Isotope Fractionation of Pesticides and Pharmaceuticals in a Mesoscale Aquifer Model.

PubMed

Schürner, Heide K V; Maier, Michael P; Eckert, Dominik; Brejcha, Ramona; Neumann, Claudia-Constanze; Stumpp, Christine; Cirpka, Olaf A; Elsner, Martin

2016-06-07

Compound-specific isotope analysis (CSIA) receives increasing interest for its ability to detect natural degradation of pesticides and pharmaceuticals. Despite recent laboratory studies, CSIA investigations of such micropollutants in the environment are still rare. To explore the certainty of information obtainable by CSIA in a near-environmental setting, a pulse of the pesticide bentazone, the pesticide metabolite 2,6-dichlorobenzamide (BAM), and the pharmaceuticals diclofenac and ibuprofen was released into a mesoscale aquifer with quasi-two-dimensional flow. Concentration breakthrough curves (BTC) of BAM and ibuprofen demonstrated neither degradation nor sorption. Bentazone was transformed but did not sorb significantly, whereas diclofenac showed both degradation and sorption. Carbon and nitrogen CSIA could be accomplished in similar concentrations as for "traditional" priority pollutants (low μg/L range), however, at the cost of uncertainties (0.4-0.5‰ (carbon), 1‰ (nitrogen)). Nonetheless, invariant carbon and nitrogen isotope values confirmed that BAM was neither degraded nor sorbed, while significant enrichment of (13)C and in particular (15)N corroborated transformation of diclofenac and bentazone. Retardation of diclofenac was reflected in additional (15)N sorption isotope effects, whereas isotope fractionation of transverse dispersion could not be identified. These results provide a benchmark on the performance of CSIA to monitor the reactivity of micropollutants in aquifers and may guide future efforts to accomplish CSIA at even lower concentrations (ng/L range).

In Situ Immobilization of Selenium in Sediment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moore, Robert C.; Stewart, Thomas Austin

2014-09-01

This project focused on the use of a sorbent, carbonated apatite, to immobilize selenium in the environment. It is know that apatite will sorb selenium and based on the mechanism of sorption it is theorized that carbonated apatite will be more effective that pure apatite. Immobilization of selenium in the environment is through the use of a sorbent in a permeable reactive barrier (PRB). A PRB can be constructed by trenching and backfill with the sorbent or in the case of apatite as the sorbent formed in situ using the apatite forming solution of Moore (2003, 2004). There is verymore » little data on selenium sorption by carbonated apatite in the literature. Therefore, in this work, the basic sorptive properties of carbonated apatite were investigated. Carbonated apatite was synthesized by a precipitation method and characterized. Batch selenium kinetic and equilibrium experiments were performed. The results indicate the carbonated apatite contained 9.4% carbonate and uptake of selenium as selenite was rapid; 5 hours for complete uptake of selenium vs. more than 100 hours for pure hydroxyapatite reported in the literature. Additionally, the carbonated apatite exhibited significantly higher distribution coefficients in equilibrium experiments than pure apatite under similar experimental conditions. The next phase of this work will be to seek additional funds to continue the research with the goal of eventually demonstrating the technology in a field application.« less

High adsorption performance for As(III) and As(V) onto novel aluminum-enriched biochar derived from abandoned Tetra Paks.

PubMed

Ding, Zhuhong; Xu, Xuebin; Phan, Thihongnhung; Hu, Xin; Nie, Guangze

2018-06-12

In order to develop promising sorbents for value-added application of solid wastes, low-cost aluminum-enriched biochar was prepared from abandoned Tetra Pak used to hold milks, a paper-polyethylence-Al foil laminated package box, after acid pretreatment and subsequent slow pyrolysis under an oxygen-limited environment at 600 °C. The basic physicochemical properties of the resultant biochar were characterized and the sorption performance of aqueous As(III) and As(V) was investigated via batch and column sorption experiments. Carbon (49.1%), Ca (7.41%) and Al (13.5%) were the most abundant elements in the resultant biochar; and the specific surface area and the pH value at the point of zero charge (pHPZC) were 174 m 2  g -1 and 9.3, respectively. Batch sorption showed excellent sorption performance for both As(III) (24.2 mg g -1 ) and As(V) (33.2 mg g -1 ) and experimental data were fitted well with Langmuir model for the sorption isotherms and pseudo-second order kinetic model for the sorption kinetics. The residual concentrations of As(V) after sorption were below the limited value of arsenic in WHO Guidelines for Drinking water Quality (0.01 mg L -1 ) even if coexistence of PO 4 3- . Column sorption confirmed the high sorption performance for As(III) and As(V). So the slow pyrolysis of abandoned Tetra Paks as low-cost and value-added sorbents is a sustainable strategy for solid waste disposal and wastewater treatment. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sorption behaviour of nonylphenol and nonylphenol monoethoxylate in soils.

PubMed

Milinovic, J; Lacorte, S; Rigol, A; Vidal, M

2015-11-01

Sorption behaviour of two alkylphenolic compounds (APCs), nonylphenol (NP) and nonylphenol monoethoxylate (NP1EO), was studied in five soils with contrasting characteristics. Sorption isotherms were obtained by equilibrating the soil samples with 0.01 mol L(-1) CaCl2 solutions containing different initial concentrations of NP or NP1EO. Linear fitting was generally appropriate for describing the sorption behaviour of NP and NP1EO in the soils, with the exception of two cases, for which the Freundlich model was more suitable for describing the sorption pattern of NP1EO. Solid-liquid distribution coefficients derived from sorption isotherms (Kd) varied from 24 to 1059 mL g(-1) for NP and from 51 to 740 mL g(-1) for NP1EO. For most soils, sorption Kd values were higher for NP than for NP1EO due to the higher hydrophobicity of NP. Sorption reversibility of NP and NP1EO was also tested from desorption isotherms. Desorption solid-liquid distribution coefficients (Kd,des), obtained from linear fitting, were between 130 and 1467 mL g(-1) for NP and between 24 and 1285 mL g(-1) for NP1EO. Kd,des values were higher than Kd values, which demonstrated that target compounds were irreversibly sorbed into soils, with the exception of the high desorption yield (45%) of NP1EO in the soil with the lowest content of organic matter. The fraction of soil organic carbon (FOC) was a key parameter that influenced the sorption of NP and NP1EO in soils, with logKOC values of 4.0 and 3.8, respectively. Copyright © 2014 Elsevier Ltd. All rights reserved.

Co-transport of chlordecone and sulfadiazine in the presence of functionalized multi-walled carbon nanotubes in soils

USDA-ARS?s Scientific Manuscript database

Batch and saturated soil column experiments were conducted to investigate sorption and mobility of two 14C-labeled contaminants, the hydrophobic chlordecone (CLD) and the readily water-soluble sulfadiazine (SDZ), in the absence or presence of functionalized multi-walled carbon nanotubes (MWCNTs). Th...

Use of modified pine bark for removal of pesticides from stormwater runoff

Treesearch

Mandla A. Tshabalala

2003-01-01

Pesticide entrainment in stormwater runoff can contribute to non-point source pollution of surface waters. Granular activated carbon has been successfully used for removing pesticides from wastewater. However, implementation of granular activated carbon sorption media in stormwater filtration systems comes with high initial capital investment and operating costs....

Do goethite surfaces really control the transport and retention of multi-walled carbon nanotubes in chemically heterogeneous porous media?

USDA-ARS?s Scientific Manuscript database

Transport and retention behavior of multiwalled carbon nanotubes (MWCNTs) was studied in mixtures of negatively charged quartz sand (QS) and positively charged goethite-coated sand (GQS) to assess the role of chemical heterogeneity. The linear equilibrium sorption model provided a good description o...

Preparation of porous carbons from polymeric precursors modified with acrylated kraft lignin

NASA Astrophysics Data System (ADS)

Sobiesiak, M.

2016-04-01

The presented studies concern the preparation of porous carbons from a BPA.DA-St polymer containing acrylated kraft lignin as a monomer. The porous polymeric precursor in the form of microspheres was synthesized in suspension polymerization process. Next samples of the polymer were impregnated with acetic acid or aqueous solution of acetates (potassium or ammonia), dried and carbonised in nitrogen atmosphere at 450°C. After carbonization microspherical shape of the materials was remained, that is desired feature for potential application in chromatography or SPE technique. Chemical and textural properties of the porous carbon adsorbents were characterized using infrared spectroscopy (ATR-FTIR), thermogravimetry analyses with mass spectrometry of released gases (TG-MS) and nitrogen sorption experiments. The presented studies revealed the impregnation is useful method for development of porous structure of carbonaceous materials. The highest values of porous structure parameters were obtained when acetic acid and ammonium acetate were used as impregnating substances. On the surface of the materials oxygen functional groups are present that is important for specific interactions during sorption processes. The highest contents of functionalities were observed for carbon BPA.DA-St-LA-C-AcNH4.

Significant solubility of carbon dioxide in Soluplus® facilitates impregnation of ibuprofen using supercritical fluid technology.

PubMed

Obaidat, Rana; Alnaief, Mohammed; Jaeger, Philip

2017-04-13

Treatment of Soluplus ® with supercritical carbon dioxide allows promising applications in preparing dispersions of amorphous solids. Several characterization techniques were employed to reveal this effect, including CO 2 gas sorption under high pressure and physicochemical characterizations techniques. A gravimetric method was used to determine the solubility of carbon dioxide in the polymer at elevated pressure. The following physicochemical characterizations were used: thermal analysis, X-ray diffraction, Fourier transform, infrared spectroscopy and scanning electron microscopy. Drug loading of the polymer with ibuprofen as a model drug was also investigated. The proposed treatment with supercritical carbon dioxide allows to prepare solid solutions of Soluplus ® in less than two hours at temperatures that do not exceed 45 °C, which is a great advantage to be used for thermolabile drugs. The advantages of using this technology for Soluplus ® formulations lies behind the high sorption capability of carbon dioxide inside the polymer. This will ensure rapid diffusion of the dissolved/dispersed drug inside the polymer under process conditions and rapid precipitation of the drug in the amorphous form during depressurization accompanied by foaming of the polymer.

Selection of best impregnated palm shell activated carbon (PSAC) for simultaneous removal of SO2 and NOx.

PubMed

Sumathi, S; Bhatia, S; Lee, K T; Mohamed, A R

2010-04-15

This work examines the impregnated carbon-based sorbents for simultaneous removal of SO(2) and NOx from simulated flue gas. The carbon-based sorbents were prepared using palm shell activated carbon (PSAC) impregnated with several metal oxides (Ni, V, Fe and Ce). The removal of SO(2) and NOx from the simulated flue gas was investigated in a fixed-bed reactor. The results showed that PSAC impregnated with CeO(2) (PSAC-Ce) reported the highest sorption capacity among other impregnated metal oxides for the simultaneous removal of SO(2) and NOx. PSAC-Ce showed the longest breakthrough time of 165 and 115 min for SO(2) and NOx, respectively. The properties of the pure and impregnated PSAC were analyzed by BET, FTIR and XRF. The physical-chemical features of the PSAC-Ce sorbent indicated a catalytic activity in both the sorption of SO(2) and NOx. The formation of both sulfate (SO(4)(2-)) and nitrate (NO(3-)) species on spent PSAC-Ce further prove the catalytic role played by CeO(2). 2009 Elsevier B.V. All rights reserved.

The potential applications of using compost chars for removing the hydrophobic herbicide atrazine from solution

USGS Publications Warehouse

Tsui, L.; Roy, W.R.

2008-01-01

One commercial compost sample was pyrolyzed to produce chars as a sorbent for removing the herbicide atrazine from solution. The sorption behavior of compost-based char was compared with that of an activated carbon derived from corn stillage. When compost was pyrolyzed, the char yield was greater than 45% when heated under air, and 52% when heated under N2. In contrast, when the corn stillage was pyrolyzed under N2, the yield was only 22%. The N2-BET surface area of corn stillage activated carbon was 439 m2/g, which was much greater than the maximum compost char surface area of 72 m2/g. However, the sorption affinity of the compost char for dissolved atrazine was comparable to that of the corn stillage activated carbon. This similarity could have resulted from the initial organic waste being subjected to a relatively long period of thermal processes during composting, and thus, the compost was more thermally stable when compared with the raw materials. In addition, microorganisms transformed the organic wastes into amorphous humic substances, and thus, it was likely that the microporisity was enhanced. Although this micropore structure could not be detected by the N2-BET method, it was apparent in the atrazine sorption experiment. Overall, the experimental results suggested that the compost sample in current study was a relatively stable material thermally for producing char, and that it has the potential as a feed stock for making high-quality activated carbon. ?? 2007 Elsevier Ltd. All rights reserved.

Adsorption mechanism of different organic chemicals on fluorinated carbon nanotubes.

PubMed

Li, Hao; Zheng, Nan; Liang, Ni; Zhang, Di; Wu, Min; Pan, Bo

2016-07-01

Multi-walled carbon nanotubes (MC) were fluorinated by a solid-phase reaction method using polytetrafluoroethylene (PTFE). The surface alteration of carbon nanotubes after fluorination (MC-F) was confirmed based on surface elemental analysis, TEM and SEM. The incorporation of F on MC surface was discussed as F incorporation on carbon defects, replacement of carboxyl groups, as well as surface coating of PTFE. The adsorption performance and mechanisms of MC-F for five kinds of representative organic compounds: sulfamethoxazole (SMX), ofloxacin (OFL), norfloxacin (NOR), bisphenol a (BPA) and phenanthrene (PHE) were investigated. Although BET-N2 surface area of the investigated CNTs decreased after fluorination, the adsorption of all five chemicals increased. Because of the glassification of MC-F surface coating during BET-N2 surface area measurement, the accessible surface area of MC-F was underestimated. Desorption hysteresis was generally observed in all the sorption systems in this study, and the desorption hysteresis of MC-F were stronger than the pristine CNTs. The enhanced adsorption of MC-F may be attributed the pores generated on the coated PTFE and the dispersed CNT aggregates due to the increased electrostatic repulsion after fluorination. The rearrangement of the bundles or diffusion of the adsorbates in MC-F inner pores were the likely reason for the strong desorption hysteresis of MC-F. The butterfly structure of BPA resulted in its high sorption and strong desorption hysteresis. The exothermic sorption character of OFL on CNTs resulted in its strong desorption hysteresis. Copyright © 2016 Elsevier Ltd. All rights reserved.

Biodegradation of sorbed chemicals in soil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scow, K.M.; Fan, S.; Johnson, C.

Rates of biodegradation of sorbed chemicals are usually lower in soil than in aqueous systems, in part because sorption reduces the availability of the chemical to microorganisms. Biodegradation, sorption, and diffusion occur simultaneously and are tightly coupled. In soil, the rate of biodegradation is a function of a chemical`s diffusion coefficient, sorption partition coefficient, the distance it must diffuse from the site of sorption to microbial populations that can degrade it, and its biodegradation rate constant. A model (DSB model) was developed that describes biodegradation of chemicals limited in the availability by sorption and diffusion. Different kinetics expressions describe biodegradationmore » depending on whether the reaction is controlled by mass transfer (diffusion and sorption) or the intrinsic biodegradation rate, and whether biodegradation begins during or after the majority of sorption has occurred. We tested the hypothesis that there is a direct relationship between how strongly a chemical is sorbed and the chemical`s biodegradation rate. In six soils with different organic carbon contents, there was no relationship between the extent or rate of biodegradation and the sorption partition coefficient for phenanthrene. Aging of phenanthrene residues in soil led to a substantial reduction in the rate of biodegradation compared to biodegradation rates of recently added phenanthrene. Considerable research has focused on identification and development of techniques for enhancing in situ biodegradation of sorbed chemicals. Development of such techniques, especially those involving inoculation with microbial strains, should consider physical mass transfer limitations and potential decreases in bioavailability over time. 4 refs., 3 figs., 1 tab.« less

The effect of humic acid on uranyl sorption onto bentonite at trace uranium levels.

PubMed

Ivanov, Peter; Griffiths, Tamara; Bryan, Nick D; Bozhikov, Gospodin; Dmitriev, Serguei

2012-11-01

The effect of humic acid (HA) on U(VI) sorption on bentonite was studied in batch experiments at room temperature and ambient atmosphere at a (237)U(VI) concentration of 8.4 × 10(-11) M and HA concentration of 100 mg L(-1). The distribution of U(VI) between the liquid and solid phases was studied as a function of pH and ionic strength both in the absence and presence of HA. It was shown that the uranyl sorption on bentonite is strongly dependent on pH and the presence of humics, and the effect of the addition order was negligible. In the absence of HA an enhancement in the uptake with increasing pH was observed and a sharp sorption edge was found to take place between pH 3.2 and 4.2. The presence of HA slightly increases uranium(VI) sorption at low pH and curtails it at moderate pH, compared to the absence of HA. In the basic pH range for both the presence and absence of HA the sorption of uranium is significantly reduced, which could be attributed to the formation of soluble uranyl carbonate complexes. The influence of ionic strength on U(VI) and HA uptake by bentonite were investigated in the range of 0.01-1.0 M, and while there was an enhancement in the sorption of humic acid with increasing ionic strength, no significant effect of the ionic strength on the U(VI) sorption was observed in both the absence and presence of HA.

Sorption and degradation of pharmaceuticals and personal care products (PPCPs) in soils.

PubMed

Yu, Yong; Liu, Yin; Wu, Laosheng

2013-06-01

Pharmaceuticals and personal care products (PPCPs) are one class of the most urgent emerging contaminants, which have drawn much public and scientific concern due to widespread contamination in aquatic environment. Most studies on the environmental fate and behavior of PPCPs have focused on nonsteroidal anti-inflammatory drugs. Some other compounds with high concentrations were less mentioned. In this study, sorption and degradation of five selected PPCPs, including bisphenol A (BPA), carbamazepine (CBZ), gemfibrozil (GFB), octylphenol (OP), and triclosan (TCS) have been investigated using three different soils. Sorption isotherms of all tested PPCPs in soils were well described by Freundlich equation. TCS and OP showed moderate to strong sorption, while the sorption of GFB and CBZ in soils was negligible. Degradation of PPCPs in three soils was generally fitted first-order exponential decay model, with half-lives (t 1/2) varying from 9.8 to 39.1 days. Sterilization could prolong the t 1/2 of PPCPs in soil, indicating that microbial activity played an important role in the degradation of these chemicals in soils. Degradation of PPCPs in soils was also influenced by the soil organic carbon (f oc) contents. Results from our data show that sorption to the soils varied among the different PPCPs, and their sorption affinity on soil followed the order of TCS > OP > BPA > GFB > CBZ. The degradation of the selected PPCPs in soil was influenced by the microbial activity and soil type. The poor sorption and relative persistence of CBZ suggest that it may pose a high leaching risk for groundwater contamination when recycled for irrigation.

Comparative study of selenite adsorption on carbon based adsorbents and activated alumina.

PubMed

Jegadeesan, G; Mondal, K; Lalvani, S B

2003-08-01

The sorption characteristics of carbon-based adsorbents such as activated carbon and chitin for the removal of selenite, Se (IV), an anionic, hazardous contaminant, are compared with those of alpha and gamma alumina. Batch experiments were conducted to determine the influence of pH, concentration of adsorbate, adsorbent loading and temperature on the sorption characteristics of the adsorbents. Generally, low pH of the solution resulted in favorable selenium removal. With the exception of activated carbon, uptakes decreased with increase in temperature. In comparison, chitin was found to be far less effective for the removal of Se (IV) from aqueous solutions. The data also showed that gamma alumina provided higher selenium removal percentages (99%) compared to alpha alumina (94%), activated carbon (87%) and chitin (49%). The selenite removal was found to decrease with increasing initial Se (IV) concentration in the solution. Adsorption capacities of the adsorbents are reported in terms of their Langmuir adsorption isotherms. The adsorption capacity (on unit mass basis) of the adsorbents for selenite is in the order: chitin (specific area (sa) = 9.58 m2 g(-1)) < activated carbon (sa = 96.37 m2 g(-1)) < alpha alumina (sa = 6 m2 g(-1)) < gamma alumina (sa = 150 m2 g(-1)).

Preparation, microstructure and hydrogen sorption properties of nanoporous carbon aerogels under ambient drying.

PubMed

Tian, H Y; Buckley, C E; Mulè, S; Paskevicius, M; Dhal, B B

2008-11-26

Organic aerogels are prepared by the sol-gel method from polymerization of resorcinol with furfural. These aerogels are further carbonized in nitrogen in order to obtain their corresponding carbon aerogels (CA); a sample which was carbonized at 900 °C was also activated in a carbon dioxide atmosphere at 900 °C. The chemical reaction mechanism and optimum synthesis conditions are investigated by means of Fourier transform infrared spectroscopy and thermoanalyses (thermogravimetric/differential thermal analyses) with a focus on the sol-gel process. The carbon aerogels were investigated with respect to their microstructures, using small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and nitrogen adsorption measurements at 77 K. SAXS studies showed that micropores with a radius of gyration of <0.35 ± 0.07 to 0.55 ± 0.05 nm were present, and TEM measurements and nitrogen adsorption showed that larger mesopores were also present. Hydrogen storage properties of the CA were also investigated. An activated sample with a Brunauer-Emmett-Teller surface area of 1539 ± 20 m(2) g(-1) displayed a reasonably high hydrogen uptake at 77 K with a maximum hydrogen sorption of 3.6 wt% at 2.5 MPa. These results suggest that CA are promising candidate hydrogen storage materials.

Preparation, microstructure and hydrogen sorption properties of nanoporous carbon aerogels under ambient drying

NASA Astrophysics Data System (ADS)

Tian, H. Y.; Buckley, C. E.; Mulè, S.; Paskevicius, M.; Dhal, B. B.

2008-11-01

Organic aerogels are prepared by the sol-gel method from polymerization of resorcinol with furfural. These aerogels are further carbonized in nitrogen in order to obtain their corresponding carbon aerogels (CA); a sample which was carbonized at 900 °C was also activated in a carbon dioxide atmosphere at 900 °C. The chemical reaction mechanism and optimum synthesis conditions are investigated by means of Fourier transform infrared spectroscopy and thermoanalyses (thermogravimetric/differential thermal analyses) with a focus on the sol-gel process. The carbon aerogels were investigated with respect to their microstructures, using small angle x-ray scattering (SAXS), transmission electron microscopy (TEM) and nitrogen adsorption measurements at 77 K. SAXS studies showed that micropores with a radius of gyration of <0.35 ± 0.07 to 0.55 ± 0.05 nm were present, and TEM measurements and nitrogen adsorption showed that larger mesopores were also present. Hydrogen storage properties of the CA were also investigated. An activated sample with a Brunauer-Emmett-Teller surface area of 1539 ± 20 m2 g-1 displayed a reasonably high hydrogen uptake at 77 K with a maximum hydrogen sorption of 3.6 wt% at 2.5 MPa. These results suggest that CA are promising candidate hydrogen storage materials.

Nanoscale carbon materials from hydrocarbons pyrolysis: Structure, chemical behavior, utilisation for non-aqueous supercapacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Savilov, Serguei V., E-mail: savilov@chem.msu.ru; Strokova, Natalia E.; Ivanov, Anton S.

Highlights: • N-doped and regular carbon nanomaterials were obtained by pyrolitic technique. • Dynamic vapor sorption of different solvents reveals smaller S{sub BET} values. • Steric hindrance and specific chemical interactions are the reasons for this. • Nitrogen doping leads to raise of capacitance and coulombic efficiency with non-aqueous N-containing electrolyte. - Abstract: This work systematically studies adsorption properties of carbon nanomaterials that are synthesized through hydrocarbons that is a powerful technique to fabricate different kinds of carbon materials, e.g., nanotubes, nanoshells, onions, including nitrogen substituted. The adsorption properties of the as-synthesized carbons are achieved by low temperature nitrogen adsorptionmore » and organic vapors sorption. Heptane, acetonitrile, water, ethanol, benzene and 1-methylimidazole, which are of great importance for development of supercapacitors, are used as substrates. It is discovered that while nitrogen adsorption reveals a high specific surface area, this parameter for most of organic compounds is rather small depending not only on the size of its molecule but also on chemical interactions for a pair adsorbent–adsorbate. The experimental values of heat of adsorption for carbon and N-substituted structures, when Coulomb cross-coupling of nitrogen atoms in adsorbent and adsorbate takes place, confirms this supposition.« less

Interactions of triclosan, gemfibrozil and galaxolide with biosolid-amended soils: Effects of the level and nature of soil organic matter.

PubMed

Usyskin, Alla; Bukhanovsky, Nadezhda; Borisover, Mikhail

2015-11-01

Triclosan, gemfibrozil and galaxolide, representing acidic and non-ionized hydrophobic organic compounds, are biologically active and can be accumulated during wastewater treatment in sewage sludge. The interactions of these substances with the soils amended by sewage sludge-originating biosolids may control their environmental fate. Therefore, the sorption of three organic compounds was studied in dune sand, loess soil, clay soil and mixtures of these media with three different sewage sludge-originating biosolids that were incubated under aerobic conditions for 6 months. For each compound, 15 sorption isotherms were produced at pH 7.8-8.0. The sorption of triclosan and gemfibrozil on sand-containing sorbents was examined also under acidic conditions. In some soil series, the compound's Freundlich constants (KF) are linearly related to the soil organic carbon (OC) content. Notably, for a given OC content, the sand-containing sorbents tend to demonstrate enhanced interactions with triclosan and galaxolide. This may be related with more hydrophobic and/or less rigid soil organic matter (SOM) as compared with the clay-containing soils, implying indirect effects of minerals. Generally the OC-normalized KF vary among different soil-biosolid combinations which is explained by the differences in the composition and properties of SOM, and is also contributed by the non-zero intercepts of the linear KF upon soil OC dependencies. The negative intercepts suggest that below a certain OC level no considerable organic compound-soil interactions would occur. Interactions of molecular and anionic forms of triclosan with a sand-containing sorbent may be comparable, but interactions involving gemfibrozil molecules could be stronger than interactions involving its anion. Copyright © 2015 Elsevier Ltd. All rights reserved.

Boronization in textor

NASA Astrophysics Data System (ADS)

Winter, J.; Esser, H. G.; Könen, L.; Philipps, V.; Reimer, H.; Seggern, J. v.; Schlüter, J.; Vietzke, E.; Waelbroeck, F.; Wienhold, P.; Banno, T.; Ringer, D.; Vepřek, S.

1989-04-01

The liner and limiters of TEXTOR have been coated in situ with a boron containing carbon film using a RG discharge in a throughflow of 0.8 He + 0.1 B 2H 6 +0.1 CH 4. The average film thickness was 30-50 nm, the ratio of boron and carbon in the layer was about 1:1 according to Auger Electron Spectroscopy. Subsequent tokamak discharges are characterized by a small fraction of radiated power (< 0.3) even during high power ICRF heating (2.6 MW, 1.6 s). A concomitant strong increase of the convective power loading of the limiters is observed. Values of Z eff lower than 1.2 are derived from conductivity measurements. The most prominent change in the impurity concentration compared to good conditions in a carbonized surrounding is measured for oxygen. The value OVI/ n¯e of the OVI intensity normalized to the averaged plasma density overlinene decreases by more than a factor of four. The decrease in the oxygen content manifests itself also as a reduction of the CO and CO 2 partial pressures measured during and after the discharge with a sniffer probe. The carbon levels are reduced by a factor of about two as measured by the normalized intensity CII/ overlinene of the CII line and via the ratio of the C fluxes and deuterium fluxes measured at the limiter (CI/D α). The wall shows a pronounced sorption of hydrogen from the plasma, easing the density control and the establishment of low recycling conditions. The beneficial conditions did not show a significant deterioration during more than 200 discharges, including numerous shots at ICRH power levels > 2 MW.

Understanding mechanisms to predict and optimize biochar for agrochemical sorption

NASA Astrophysics Data System (ADS)

Hall, Kathleen; Gámiz, Beatriz; Cox, Lucia; Spokas, Kurt; Koskinen, William

2017-04-01

The ability of biochars to bind various organic compounds has been widely studied due to the potential effects on pesticide fate in soil and interest in the adoption of biochar as a "low-cost" filter material. However, the sorptive behaviors of biochars are extremely variable and much of the reported data is limited to specific biochar-chemical interactions. The lack of knowledge regarding biochar sorption mechanisms limits our current ability to predict and optimize biochar's use. This work unveils mechanistic drivers of organic pesticide sorption on biochars through targeted alteration of biochar surface chemistry. Changes in the quantity and type of functional groups on biochars and other black carbon materials were achieved through treatments with H2O2, and CO2, and characterized using Fourier transform infrared spectroscopy and scanning electron microscope (SEM/EDX). The sorption capacities of these treated biochars were subsequently measured to evaluate the effects of different surface moieties on the binding of target herbicides cyhalofop acid ((R)-2-[4-(4-cyano-2-fluorophenoxy)phenoxy]propionic acid) and clomazone (2-[(2-chlorophenyl)methyl]-4,4-dimethyl-1,2-oxazolidin-3-one). Sorption of both herbicides on the studied biochars increased following H2O2 activation; however, the influence of the H2O2 activation on sorption was more pronounced for cyhalofop acid (pKa = 3.9) than clomazone, which is non-ionizable. Increased cyhalofop acid sorption on H2O2 treated biochars can be attributed to the increase in oxygen containing functional groups as well as the decrease in biochar pH. In contrast, CO2 activation reduced the sorption of cyhalofop acid compared to untreated biochar. FTIR data suggest the reduced sorption on CO2 -treated biochar was due to the removal of surface carboxyl groups, further supporting the role of specific functionality in the sorption of ionizable herbicides. Results from this work offer insight into the mechanisms of sorption and provide the basis to simultaneously evaluate the overall effectiveness of surface activation treatments. In addition, we are currently examining the influence of specific biochar alterations via activation on nitrate sorption and uptake; forthcoming results will also be presented.

Ethylbenzene Removal by Carbon Nanotubes from Aqueous Solution

PubMed Central

Bina, Bijan; Pourzamani, Hamidreza; Rashidi, Alimorad; Amin, Mohammad Mehdi

2012-01-01

The removal of ethylbenzene (E) from aqueous solution by multiwalled, single-walled, and hybrid carbon nanotubes (MWCNTs, SWCNTs, and HCNTs) was evaluated for a nanomaterial dose of 1 g/L, concentration of 10–100 mg/L, and pH 7. The equilibrium amount removed by SWCNTs (E: 9.98 mg/g) was higher than by MWCNTs and HCNTs. Ethylbenzene has a higher adsorption tendency on CNTs, so that more than 98% of it adsorbed in first 14 min, which is related to the low water solubility and the high molecular weight. The SWCNTs performed better for ethylbenzene sorption than the HCNTs and MWCNTs. Isotherms study indicates that the BET isotherm expression provides the best fit for ethylbenzene sorption by SWCNTs. Carbon nanotubes, specially SWCNTs, are efficient and rapid adsorbents for ethylbenzene which possess good potential applications to maintain high-quality water. Therefore, it could be used for cleaning up environmental pollution to prevent ethylbenzene borne diseases. PMID:22187576

Sorption and bioaccumulation behavior of multi-class hydrophobic organic contaminants in a tropical marine food web.

PubMed

Zhang, Hui; Kelly, Barry C

2018-05-01

While numerous studies have demonstrated the environmental behavior of legacy persistent organic pollutants (POPs), such as polychlorinated biphenyls (PCBs) and organochlorine pesticides (OCPs), information regarding sorption and bioaccumulation potential of other widely used organic chemicals such as halogenated flame retardants (HFRs) is limited. This study involved a comprehensive field investigation of multi-class hydrophobic organic contaminants (HOCs) in environmental media and fish in Singapore Strait, an important tropical maritime strait in Southeast Asia. In total, 90 HOCs were analyzed, including HFRs, synthetic musks, PCBs, OCPs, as well as triclosan and methyl triclosan. The results show that the organic carbon normalized sediment-seawater distribution ratios (C SED /C WD ) of the studied compounds are comparable to the organic carbon-water partition coefficients (K OC ), over a log K OC range of approximately 4-11. The observed species-specific bioaccumulation factors (BAFs), biota-sediment accumulation factors (BSAFs), organism-environment media fugacity ratios (f FISH /f WD and f FISH /f SED ) and trophic magnification factors (TMFs) indicate that legacy POPs and PBDE 47 show bioaccumulation behavior in this tropical marine ecosystem, while triclosan, tonalide, dodecachlorodimethanodibenzocyclooctane stereoisomers (DDC-COs), and hexabromocyclododecanes (HBCDDs) do not. Methyl triclosan and galaxolide exhibit moderate biomagnification. Tetrabromobisphenol A (TBBPA) and 1,2-bis (2,4,6-tribromophenoxy)ethane (BTBPE) were detected in environmental media but not in any of the organisms, suggesting low bioaccumulation potential of these flame retardants. The apparently low bioaccumulation potential of the studied HFRs and synthetic musks is likely because of metabolic transformation and/or reduced bioavailability due to the hydrophobic nature of these compounds. Copyright © 2018 Elsevier Ltd. All rights reserved.

Influence of carbon and metal oxide nanomaterials on aqueous concentrations of the munition constituents cyclotrimethylenetrinitramine (RDX) and tungsten.

PubMed

Brame, Jonathon A; Kennedy, Alan J; Lounds, Christopher D; Bednar, Anthony J; Alvarez, Pedro J J; Scott, Andrea M; Stanley, Jacob K

2014-05-01

There is an increasing likelihood of interactions between nanomaterials and munitions constituents in the environment resulting from the use of nanomaterials as additives to energetic formulations and potential contact in waste streams from production facilities and runoff from training ranges. The purpose of the present research was to determine the ability of nano-aluminum oxide (Al(2)O(3)) and multiwalled carbon nanotubes (MWCNTs) to adsorb the munitions constituents cyclotrimethylenetrinitramine (RDX) and tungsten (W) from aqueous solution as a first step in determining the long-term exposure, transport, and bioavailability implications of such interactions. The results indicate significant adsorption of RDX by MWCNTs and of W by nano-Al(2)O(3) (but not between W and MWCNT or RDX and nano-Al(2)O(3)). Kinetic sorption and desorption investigations indicated that the most sorption occurs nearly instantaneously (<5 min), with a relatively slower, secondary binding leading to statistically significant but relatively smaller increases in adsorption over 30 d. The RDX sorption that occurred during the initial interaction was irreversible, with long-term, reversible sorption likely the result of a secondary interaction; as interaction time increased, however, the portion of W irreversibly sorbed onto nano-Al(2)O(3) also increased. The present study shows that strong interactions between some munitions constituents and nanomaterials following environmental release are likely. Time-dependent binding has implications for the bioavailability, migration, transport, and fate of munitions constituents in the environment. © 2014 SETAC.

Sorption of phenanthrene and benzene on differently structural kerogen: important role of micropore-filling.

PubMed

Zhang, Yulong; Ma, Xiaoxuan; Ran, Yong

2014-02-01

Shale was thermally treated to obtain a series of kerogen with varied maturation. Their chemical, structural and porous properties were related to the sorption and/or desorption behaviors of phenanthrene and benzene. As the treatment temperature increases, aliphatic and carbonyl carbon of the kerogen samples decrease, while their aromaticity and maturation increase. Meanwhile, the isothermal nonlinearity of phenanthrene and benzene increases whereas the sorption capacity and micropore adsorption volumes (Vo,d) initially increase and then decrease. The Vo,d of benzene is significantly correlated with, but higher than that of phenanthrene, suggesting similar micropore filling mechanism and molecular sieve effect. The benzene desorption exhibits hysteresis, which is related to the pore deformation of the kerogen and the entrapment of solute in the kerogen matrix. The Vo,d of phenanthrene and benzene on the kerogen samples accounts for 23-46% and 36-65% of the maximum sorption volumes, respectively, displaying the importance of the micropore filling. Copyright © 2013 Elsevier Ltd. All rights reserved.

Different effects of copper (II), cadmium (II) and phosphate on the sorption of phenanthrene on the biomass of cyanobacteria.

PubMed

Tao, Yuqiang; Li, Wei; Xue, Bin; Zhong, Jicheng; Yao, Shuchun; Wu, Qinglong

2013-10-15

Due to the large surface area and high organic carbon content of cyanobacteria, organic contaminants can be readily sorbed on cyanobacteria during algal blooms, and then be transferred to the food web. This process is likely to be affected by the coexisting metals and nutrients, however, the possible impacts remain unclear. Effects of Cu(2+), Cd(2+), and phosphate on the sorption of phenanthrene on cyanobacterial biomass collected from an algal bloom were therefore studied. Continuous decrease in phenanthrene sorption was observed in the presence of low concentrations of Cu(2+), and Cd(2+) (<0.04 mmol L(-1)), because Cu(2+) and Cd(2+) were coadsorbed with phenanthrene on the surface of cyanobacteria as suggested by scanning electron microscopy-energy dispersive X-ray (SEM-EDX) and Fourier transform infrared (FTIR) analyses. Phenanthrene sorption began to increase with the further increase in Cu(2+) concentration, but remained lower than that in the absence of Cu(2+). This increase in sorption was ascribed to the cation-π interaction between Cu(2+) and phenanthrene, as suggested by the enhanced ultraviolet absorbance at 251 nm. In contrast, sorption rebounding of phenanthrene did not occur in the presence of higher concentrations of Cd(2+). The different effects of Cu(2+) and Cd(2+) on phenanthrene sorption were attributed to that Cd(2+) required much more energy than Cu(2+) to form cation-π complexes with phenanthrene in the solutions. Phenanthrene sorption decreased continuously with the increase in phosphate concentration. Phosphate blocked the binding sites, modified the cell morphology, and increased the negative charge as well as the hydrophilicity of the cyanobacterial surface, thereby suppressing phenanthrene sorption. This study indicates that sorption of aromatic organic compounds by cyanobacteria could be significantly alerted by concentrations and properties of the coexisting transition metals and phosphates, which may subsequently affect their transfer to the food web in eutrophic waters. Crown Copyright © 2013. Published by Elsevier B.V. All rights reserved.

A review of the distribution coefficients of trace elements in soils: influence of sorption system, element characteristics, and soil colloidal properties.

PubMed

Shaheen, Sabry M; Tsadilas, Christos D; Rinklebe, Jörg

2013-12-01

Knowledge about the behavior and reactions of separate soil components with trace elements (TEs) and their distribution coefficients (Kds) in soils is a key issue in assessing the mobility and retention of TEs. Thus, the fate of TEs and the toxic risk they pose depend crucially on their Kd in soil. This article reviews the Kd of TEs in soils as affected by the sorption system, element characteristics, and soil colloidal properties. The sorption mechanism, determining factors, favorable conditions, and competitive ions on the sorption and Kd of TEs are also discussed here. This review demonstrates that the Kd value of TEs does not only depend on inorganic and organic soil constituents, but also on the nature and characteristics of the elements involved as well as on their competition for sorption sites. The Kd value of TEs is mainly affected by individual or competitive sorption systems. Generally, the sorption in competitive systems is lower than in mono-metal sorption systems. More strongly sorbed elements, such as Pb and Cu, are less affected by competition than mobile elements, such as Cd, Ni, and Zn. The sorption preference exhibited by soils for elements over others may be due to: (i) the hydrolysis constant, (ii) the atomic weight, (iii) the ionic radius, and subsequently the hydrated radius, and (iv) its Misono softness value. Moreover, element concentrations in the test solution mainly affect the Kd values. Mostly, values of Kd decrease as the concentration of the included cation increases in the test solution. Additionally, the Kd of TEs is controlled by the sorption characteristics of soils, such as pH, clay minerals, soil organic matter, Fe and Mn oxides, and calcium carbonate. However, more research is required to verify the practical utilization of studying Kd of TEs in soils as a reliable indicator for assessing the remediation process of toxic metals in soils and waters. © 2013 Elsevier B.V. All rights reserved.

Linear modeling of the soil-water partition coefficient normalized to organic carbon content by reversed-phase thin-layer chromatography.

PubMed

Andrić, Filip; Šegan, Sandra; Dramićanin, Aleksandra; Majstorović, Helena; Milojković-Opsenica, Dušanka

2016-08-05

Soil-water partition coefficient normalized to the organic carbon content (KOC) is one of the crucial properties influencing the fate of organic compounds in the environment. Chromatographic methods are well established alternative for direct sorption techniques used for KOC determination. The present work proposes reversed-phase thin-layer chromatography (RP-TLC) as a simpler, yet equally accurate method as officially recommended HPLC technique. Several TLC systems were studied including octadecyl-(RP18) and cyano-(CN) modified silica layers in combination with methanol-water and acetonitrile-water mixtures as mobile phases. In total 50 compounds of different molecular shape, size, and various ability to establish specific interactions were selected (phenols, beznodiazepines, triazine herbicides, and polyaromatic hydrocarbons). Calibration set of 29 compounds with known logKOC values determined by sorption experiments was used to build simple univariate calibrations, Principal Component Regression (PCR) and Partial Least Squares (PLS) models between logKOC and TLC retention parameters. Models exhibit good statistical performance, indicating that CN-layers contribute better to logKOC modeling than RP18-silica. The most promising TLC methods, officially recommended HPLC method, and four in silico estimation approaches have been compared by non-parametric Sum of Ranking Differences approach (SRD). The best estimations of logKOC values were achieved by simple univariate calibration of TLC retention data involving CN-silica layers and moderate content of methanol (40-50%v/v). They were ranked far well compared to the officially recommended HPLC method which was ranked in the middle. The worst estimates have been obtained from in silico computations based on octanol-water partition coefficient. Linear Solvation Energy Relationship study revealed that increased polarity of CN-layers over RP18 in combination with methanol-water mixtures is the key to better modeling of logKOC through significant diminishing of dipolar and proton accepting influence of the mobile phase as well as enhancing molar refractivity in excess of the chromatographic systems. Copyright © 2016 Elsevier B.V. All rights reserved.

Enhanced Sorption of PAHs in Natural-Fire-Impacted Sediments from Oriole Lake, California

EPA Science Inventory

Surface sediment cores from Oriole Lake (CA) were analyzed for organic carbon (OC), black carbon (BC), and their δ13C isotope ratios. Sediments displayed high OC(20-25%) and increasing BC concentrations from ∼0.40% (in 1800 C.E.) to ∼0.60% dry weight (in 2000 C.E.). Petrographic...

[Bromate reduction by granular activated carbon].

PubMed

Huang, Xin; Gao, Nai-yun; Lu, Pin-pin

2007-10-01

Batch experiments were conducted to evaluate the kinetics of reducing bromate to bromide by granular activated carbon. Solution conditions were studied in details, such as pH, ionic strength, temperature and initial bromate concentration. The results showed the removal capacity of GAC was positively relevant to surface basic functional groups. The whole process was inhibited by other anions in solution and the inhibition sequence was NO3(-) > SO4(2-) > Cl(-). Pseudo-second order rate equation and intraparticle diffusion model were applied to fit the process of bromate reduction and the process of bromide formation, respectively, with regression coefficients higher than 0.97 at most cases. Bromate removal was found to be favored under conditions with low pH value and low ionic strength. Both sorption rate of bromate and formation rate of bromide were decreased, and then increased along with the increase of temperature during 15-42 degree C. In this experiment, the maximum adsorption capacity of GAC is 769.23 micromol/g (98.4 mg/g), whereas the sorption process is slow and easily influenced. It is concluded that the sorption of bromate by the micropore portion of GAC was influenced by the release of bromide.

Kinetic characteristics of Cu (II) adsorption on nano(poly)-cumulene

NASA Astrophysics Data System (ADS)

Babkin, Alexander; Neskoromnaya, Elena; Burakova, Irina; Kucherova, Ananstasia; Burakov, Alexander; Mkrtchyan, Elina

2017-11-01

The present paper considers the possibility of using a new type of nanocarbon materials for sorption - polycumulene modified with "Taunit-M" carbon nanotubes or graphene nanoplatelets. To evaluate the efficiency of these novel nanomodified materials as sorbents, the following studies were carried out: 1) determination of the optimum pH value to perform static batch sorption experiments, 2) identification of the onset of equilibrium for the adsorption of heavy metal ions (on the example of Cu(II) ions), and 3) elucidation of kinetic adsorption mechanisms. As a result of implementation of kinetic models such as external and internal diffusion, as well as pseudo-first- and pseudo-second-order and Elovich (to determine the contribution of chemisorption), rate constants for the Cu(II) adsorption were estimated. It was noted that the absorption process occurs in a mixed-diffusion mode with the influence of the limiting factor - "sorbate-sorbate" chemical interaction. The equilibrium time was found to be 45 min at the sorption capacity values of about 30.71 mg g-1 (in the case of the material containing carbon nanotubes) and about 24.7 mg g-1 (in the case of the material containing graphene nanoplatelets).

The modeling of reactive solute transport with sorption to mobile and immobile sorbents 1. Experimental evidence and model development

NASA Astrophysics Data System (ADS)

Knabner, P.; Totsche, K. U.; Kögel-Knabner, I.

Modeling carrier-influenced transport needs to take into account the reactivity of the carrier itself. This paper presents a mathematical model of reactive solute transport with sorption to mobile and immobile sorbents. The mobile sorbent is also considered to be reactive. To justify the assumptions and generality of our modeling approach, experimental findings are reviewed and analyzed. A transformation of the model in terms of total concentrations of solute and mobile sorbents is presented which simplifies the mathematical formulations. Breakthrough data on dissolved organic carbon are presented to exemplify the need to take into account the reactivity of the mobile sorbent. Data on hexachlorobiphenyl and cadmium are presented to demonstrate carrier-introduced increased mobility, whereas data on anthracene and pyrene are presented to demonstrate carrier-introduced reduced mobility. The experimental conditions leading to the different findings are pointed out. The sorption processes considered in the model are both equilibrium and nonequilibrium processes, allowing for different sorption sites and nonlinear isotherms and rate functions. Effective isotherms, which describe the sorption to the immobile sorbent in the presence of a mobile sorbent and rate functions, are introduced and their properties are discussed.

Effects of multi-walled carbon nanotubes on mineralization and mobility of nonylphenol and sodium dodecyl sulfate in agricultural soils

NASA Astrophysics Data System (ADS)

Lillotte, Julia; Marschner, Bernd; Stumpe, Britta

2014-05-01

Nanotechnology is one of the major scientific research fields in this decade. One of the most wide-spread nanomaterials are carbon based nanoparticles (CNPs) which are increasingly be used in industry. Several studies shows that CNPs are interacting with other chemical compounds and organic pollutants in the environment. It is assumed that the interactions between CNPs and organic pollutants are affected by solution and aggregate behavior. Based on the knowledge of the behavior of CNPs and organic pollutants in aquatic systems the interactions of CNPs and organic pollutants in agricultural soils have to be studied. As organic pollutants two environmental substances, nonylphenol (NP) and sodium dodecyl sulfate (SDS) were selected as model substances. They occur frequently in aqueous systems and also show different solubility behavior. As CNP representatives, two different multi-walled carbon nanotubes (MWNT) were selected. They differed either in length or outer diameter. Conclusions therefrom are to be closed the influence of length and diameter of the sorption capacity of different organic pollutants. In addition, two agricultural soils (sandy and silty soil) and one forest soil (sandy soil) were chosen. Mineralization and sorption experiments were conducted to provide information about the degradation of organic pollutants in presence of multi-walled carbon nanotubes in soils. To analyze the CNPs mineralization potential, peroxidase activity was measured. Further extraction experiments were conducted to detect the extractable part of organic pollutants. The results show that the surface area of the MWNT has a significant impact on the sorption behav-ior of NP and SDS in soils. The sorption of NP and SDS is much higher than without MWNT. However, the properties of the organic pollutants (different water solubility and hydrophobicity) are equally important and should be noted. The degradation of both pollutants is influenced by MWNT. Due to the strong sorption of NP and SDS on the MWNT, the degradation of these pollutants in soils, is slower than without MWNT. The peroxidase activity did not contribute to NP and SDS degradation. But the peroxidase activity in agricultural soils is higher than in forest soils. The extractable fraction of NP and SDS is very low and amounts to a maximum of 2 %. Due to the lower degradation of NP and SDS in the presence of MWNT a longer retention of the substances in the soils and potential toxic effects for humans and animals, as a result of plant uptake may be taken into account.

Carbon capture by sorption-enhanced water-gas shift reaction process using hydrotalcite-based material

DOE Office of Scientific and Technical Information (OSTI.GOV)

van Selow, E.R.; Cobden, P.D.; Verbraeken, P.A.

2009-05-15

A novel route for precombustion decarbonization is the sorption-enhanced water-gas shift (SEWGS) process. In this process carbon dioxide is removed from a synthesis gas at elevated temperature by adsorption. Simultaneously, carbon monoxide is converted to carbon dioxide by the water-gas shift reaction. The periodic adsorption and desorption of carbon dioxide is induced by a pressure swing cycle, and the cyclic capacity can be amplified by purging with steam. From previous studies is it known that for SEWGS applications, hydrotalcite-based materials are particularly attractive as sorbent, and commercial high-temperature shift catalysts can be used for the conversion of carbon monoxide. Tabletsmore » of a potassium promoted hydrotalcite-based material are characterized in both breakthrough and cyclic experiments in a 2 m tall fixed-bed reactor. When exposed to a mixture of carbon dioxide, steam, and nitrogen at 400{sup o}C, the material shows a breakthrough capacity of 1.4 mmol/g. In subsequent experiments the material was mixed with tablets of promoted iron-chromium shift catalyst and exposed to a mixture of carbon dioxide, carbon monoxide, steam, hydrogen, and nitrogen. It is demonstrated that carbon monoxide conversion can be enhanced to 100% in the presence of a carbon dioxide sorbent. At breakthrough, carbon monoxide and carbon dioxide simultaneously appear at the end of the bed. During more than 300 cycles of adsorption/reaction and desorption, the capture rate, and carbon monoxide conversion are confirmed to be stable. Two different cycle types are investigated: one cycle with a CO{sub 2} rinse step and one cycle with a steam rinse step. The performance of both SEWGS cycles are discussed.« less

Polymer–Metal–Organic Frameworks (polyMOFs) as Water Tolerant Materials for Selective Carbon Dioxide Separations

DOE PAGES

Zhang, Zhenjie; Nguyen, Ha Thi Hoang; Miller, Stephen A.; ...

2015-12-28

Recently, polymer–metal–organic frameworks (polyMOFs) were reported as a new class of hybrid porous materials that combine advantages of both organic polymers and crystalline MOFs. Herein, we report a bridging coligand strategy to prepare new types of polyMOFs, demonstrating that polyMOFs are compatible with additional MOF architectures besides that of the earlier reported IRMOF-1 type polyMOF. Gas sorption studies revealed that these polyMOF materials exhibited relatively high CO 2 sorption but very low N 2 sorption, making them promising materials for CO 2/N 2 separations. Furthermore, these polyMOFs demonstrated exceptional water stability attributed to the hydrophobicity of polymer ligands as wellmore » as the cross-linking of the polymer chains within the MOF.« less

Sulfamethazine Sorption to Soil: Vegetative Management, pH, and Dissolved Organic Matter Effects.

PubMed

Chu, Bei; Goyne, Keith W; Anderson, Stephen H; Lin, Chung-Ho; Lerch, Robert N

2013-01-01

Elucidating veterinary antibiotic interactions with soil is important for assessing and mitigating possible environmental hazards. The objectives of this study were to investigate the effects of vegetative management, soil properties, and >1000 Da dissolved organic matter (DOM) on sulfamethazine (SMZ) behavior in soil. Sorption experiments were performed over a range of SMZ concentrations (2.5-50 μmol L) using samples from three soils (Armstrong, Huntington, and Menfro), each planted to one of three vegetation treatments: agroforestry buffers strips (ABS), grass buffer strips (GBS), and row crops (RC). Our results show that SMZ sorption isotherms are well fitted by the Freundlich isotherm model (log = 0.44-0.93; Freundlich nonlinearity parameter = 0.59-0.79). Further investigation of solid-to-solution distribution coefficients () demonstrated that vegetative management significantly ( < 0.05) influences SMZ sorption (ABS > GBS > RC). Multiple linear regression analyses indicated that organic carbon (OC) content, pH, and initial SMZ concentration were important properties controlling SMZ sorption. Study of the two most contrasting soils in our sample set revealed that increasing solution pH (pH 6.0-7.5) reduced SMZ sorption to the Armstrong GBS soil, but little pH effect was observed for the Huntington GBS soil containing 50% kaolinite in the clay fraction. The presence of DOM (150 mg L OC) had little significant effect on the Freundlich nonlinearity parameter; however, DOM slightly reduced SMZ values overall. Our results support the use of vegetative buffers to mitigate veterinary antibiotic loss from agroecosystems, provide guidance for properly managing vegetative buffer strips to increase SMZ sorption, and enhance understanding of SMZ sorption to soil. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Sorption of polar herbicides and herbicide metabolites by biochar-amended soil.

PubMed

Dechene, Annika; Rosendahl, Ingrid; Laabs, Volker; Amelung, Wulf

2014-08-01

Biochar-amended soil has been proven to possess superior sorption capacities for several environmental pollutants compared with pure soil. However, the role of biochar in the immobilization of polar pesticides and their metabolites has hardly been tested. The aim of this study was therefore to investigate the effect of a soil amendment with biochar on the sorption of selected polar herbicides and herbicide metabolites (log Kow 0.3-<2). To simulate worst-case sorption, a sandy soil (1.7% organic matter) was amended with 1.5% biochar (fresh or composted) to determine sorption/desorption isotherms of the test compounds. One herbicide (imazamox) and three herbicide metabolites (methyl-desphenyl-chloridazon, metazachlor oxalic acid, metazachlor sulfonic acid) were tested, i.e. three anionic and one neutral polar compound. The results showed that the presence of biochar increased the sorption capacity of the soil only in the case of the uncharged compound methyl-desphenyl-chloridazon, for which the average distribution coefficients in biochar-amended soils were higher than in pure soil by a factor of 2.1-2.5. However, this effect rather seemed to reflect the increased soil organic carbon content after the addition of biochar than a preferred sorption of methyl-desphenyl-chloridazon to biochar. In the case of the three anionic compounds imazamox, metazachlor oxalic acid and metazachlor sulfonic acid, biochar amendment did not increase the sorption capacity of the soil for these compounds, presumably as a result of its negative net charge. Similarly, desorption experiments did not show any significant effect of the biochar amendment on desorption. This suggests that the potential of using biochar to mitigate the leaching of the tested polar pesticides or metabolites is limited. Copyright © 2014 Elsevier Ltd. All rights reserved.

Impact of long-term wastewater irrigation on sorption and transport of atrazine in Mexican agricultural soils.

PubMed

Müller, K; Duwig, C; Prado, B; Siebe, C; Hidalgo, C; Etchevers, J

2012-01-01

In the Mezquital Valley, Mexico, crops have been irrigated with untreated municipal wastewater for more than a century. Atrazine has been applied to maize and alfalfa grown in the area for weed control for 15 years. Our objectives were to analyse (i) how wastewater irrigation affects the filtering of atrazine, and (ii) if the length of irrigation has a significant impact. We compared atrazine sorption to Phaeozems that have been irrigated with raw wastewater for 35 (P35) and 85 (P85) years with sorption to a non-irrigated (P0) Phaeozem soil under rainfed agriculture. The use of bromide as an inert water tracer in column experiments and the subsequent analysis of the tracers' breakthrough curves allowed the calibration of the hydrodynamic parameters of a two-site non equilibrium convection-dispersion model. The quality of the irrigation water significantly altered the soils' hydrodynamic properties (hydraulic conductivity, dispersivity and the size of pores that are hydraulically active). The impacts on soil chemical properties (total organic carbon content and pH) were not significant, while the sodium adsorption ratio was significantly increased. Sorption and desorption isotherms, determined in batch and column experiments, showed enhanced atrazine sorption and reduced and slower desorption in wastewater-irrigated soils. These effects increased with the length of irrigation. The intensified sorption-desorption hysteresis in wastewater-irrigated soils indicated that the soil organic matter developed in these soils had fewer high-energy, easily accessible sorption sites available, leading to lower and slower atrazine desorption rates. This study leads to the conclusion that wastewater irrigation decreases atrazine mobility in the Mezquital valley Phaeozems by decreasing the hydraulic conductivity and increasing the soil's sorption capacity.

Improved understanding of tributyltin sorption on natural and biochar-amended sediments.

PubMed

Xiao, Xiaoyu; Sheng, G Daniel; Qiu, Yuping

2011-12-01

A poor understanding of tributyltin (TBT) sorption on sediments has hindered an accurate evaluation of its environmental fate. The present study determined TBT sorption by a freshwater sediment (BH) and a coastal marine sediment (TZ) as influenced by pH, salinity, and biochar (BC) amendment into TZ. The isotherms were essentially linear, with K(OC) values in the range of 10(4) to 10(5) L/kg. Tributyltin sorption at pH 3.56 and 8.00 occurred mainly via partitioning. It reached maxima at pH equal to its pK(a) (=6.25) because of added ion exchange. A salinity increase from 5 to 35 practical salinity units enhanced TBT sorption at pH 3.56 and 8.00 on TZ by approximately 30% and on BH by approximately 80%, ascribed to the salting-out effect that reduced the solubilities of tributyltin hydroxide (TBTOH) and tributyltin chloride (TBTCl). At pH 6.25, the same salinity increase reduced TBT sorption on TZ by approximately 20% but enhanced TBT sorption on BH by approximately 35%. This was attributed to the enhancing role of salting out and the reducing role of metal competition for ion exchange. Tributyltin was two orders of magnitude more effectively sorbed by BC than by total organic carbon of TZ, mainly because of the high level of surface area of the BC. Although BC affinity for TBT may be significantly diminished when present in TZ, it was considered to be the primary contributor to TBT sorption from water. Biochar may thus be used to immobilize TBT in sediment for potential remediation. Copyright © 2011 SETAC.

Availability of polycyclic aromatic hydrocarbons from lampblack-impacted soils at former oil-gas plant sites in California, USA.

PubMed

Hong, Lei; Luthy, Richard G

2007-03-01

Lampblack-impacted soils at former oil-gas plant sites in California, USA, were characterized to assess the sorption of polycyclic aromatic hydrocarbons (PAHs) and the concentration-dependent effects of a residual oil tar phase on sorption mechanism and availability of PAHs. Nuclear magnetic resonance spectroscopy demonstrated similar aromaticity for both lampblack carbon and the oil tar phase, with pronounced resonance signals in the range of 100 to 150 ppm. Scanning-electron microscopic images revealed a physically distinct oil tar phase, especially at high concentrations in lampblack, which resulted in an organic-like film structure when lampblack particles became saturated with the oil tar. Sorption experiments were conducted on a series of laboratory-prepared lampblack samples to systematically evaluate influences of an oil tar phase on PAH sorption to lampblack. Results indicate that the sorption of PAHs to lampblack exhibits a competition among sorption phases at low oil tar contents when micro- and mesopores are accessible. When the oil tar content increases to more than 5 to 10% by weight, this tar phase fills small pores, reduces surface area, and dominates PAH sorption on lampblack surface. A new PAH partitioning model, Kd = KLB-C(1 - ftar)alpha + ftarKtar (alpha = empirical exponent), incorporates these effects in which the control of PAH partitioning transits from being dominated by sorption in lampblack (KLB-C) to absorption in oil tar (Ktar), depending on the fraction of tar (ftar). This study illustrates the importance of understanding interactions among PAHs, oil tar, and lampblack for explaining the differences in availability of PAHs among site soils and, consequently, for refining site-specific risk assessment and establishing soil cleanup levels.

Retention and Migration of Chlorpyrifos in Aquatic Sediments and Soils

NASA Astrophysics Data System (ADS)

Gebremariam, S. Y.; Beutel, M.; Yonge, D.; Flury, M.; Harsh, J. B.

2010-12-01

The accurate description of the fate and transport of potentially toxic agricultural pesticides in sediments and soils is of great interest to environmental scientists and regulators. Of particular concern is the widely documented detection of agricultural pesticides and their byproducts in drinking water wells. This presentation discusses results of a study of the fate and transport of chlorpyrifos, a strongly hydrophobic organophosphate-pesticide, in sediments and soils collected from a range of aquatic environments. Using radio-labeled chlorpyrifos, this study is unique in its comprehensive nature and focus on aquatic sediments, for which studies involving pesticide fate and transport are limited. Study components include: (1) batch equilibrium experiments to evaluate sorption/desorption parameters; (2) kinetic and non-equilibrium sorption experiments using miniaturized flow-cells; (3) column experiments to understand patterns of pesticide break through; and (4) numerical modeling of chlorpyrifos transport through aquatic sediments and soils. Initial results show that chlorpyrifos sorption, when corrected for reversible sorption to container walls, exhibited two component sorption, a large irreversible fraction and a smaller reversible fraction that can act as a secondary source. In addition, of a wide range of soil parameters measured, organic carbon content exhibited the highest correlation with chlorpyrifos retention in cranberry field soils. Simulation models developed in this study, which account for hysteretic and nonlinear sorption, will help to better predict the fate of chlorpyrifos and other hydrophobic chemicals in sediments and soils.

Sorption and transport of five sulfonamide antibiotics in agricultural soil and soil-manure systems.

PubMed

Wang, Na; Guo, Xinyan; Xu, Jing; Hao, Lijun; Kong, Deyang; Gao, Shixiang

2015-01-01

Animal manure application is a main spreading route of veterinary antibiotics in soil and groundwater. The sorption and leaching behavior of five commonly used sulfonamides in five typical soil and soil/manure mixtures from China were investigated in this study. Results showed that the empirical Freundlich equation fits well the sorption behavior of selected sulfonamides (r(2) was between 0.803 and 0.999, 1/n was between 0.68 and 1.44), and pH and soil organic carbon (OC) were the key impact factors to sorption and leaching. Addition of manure was found to increase the Kd values of sulfonamides in five different soils, following the rules that the more polar substances, the more increased extent of sorption after manure amendment (5.87 times for sulfadiazine with Log Kow = -0.09, and 2.49 times for sulfamethoxazole with Log Kow = 0.89). When the simulated rainfall amount reached 300 mL (180 mm), sulfonamides have high migration potential to the groundwater, especially in the soil with low OC and high pH. However, manure amendment increased the sorption capacity of sulfonamides in the top layer, thus it might play a role in decreasing the mobility of sulfonamides in soils. The systematic study would be more significant to assess the ecological risks and suggest considering the influence of manure amendment for the environmental fate of antibiotics.

Thermal Stability of Goethite-Bound Natural Organic Matter Is Impacted by Carbon Loading.

PubMed

Feng, Wenting; Klaminder, Jonatan; Boily, Jean-François

2015-12-24

Dissolved natural organic matter (NOM) sorption at mineral surfaces can significantly affect the persistence of organic carbon in soils and sediments. Consequently, determining the mechanisms that stabilize sorbed NOM is crucial for predicting the persistence of carbon in nature. This study determined the effects of loadings and pH on the thermal stability of NOM associated with synthetic goethite (α-FeOOH) particle surfaces, as a proxy for NOM-mineral interactions taking place in nature. NOM thermal stability was investigated using temperature-programmed desorption (TPD) in the 30-700 °C range to collect vibration spectra of thermally decomposing goethite-NOM assemblages, and to concomitantly analyze evolved gases using mass spectrometry. Results showed that NOM thermal stability, indicated by the range of temperatures in which CO2 evolved during thermal decomposition, was greatest in unbound NOM and lowest when NOM was bound to goethite. NOM thermal stability was also loading dependent. It decreased when loadings were in increased the 0.01 to 0.42 mg C m(-2) range, where the upper value corresponds to a Langmuirian adsorption maximum. Concomitant Fourier transform infrared (FTIR) spectroscopy measurement showed that these lowered stabilities could be ascribed to direct NOM-goethite interactions that dominated the NOM binding environment. Mineral surface interactions at larger loadings involved, on the contrary, a smaller fraction of the sorbed NOM, thus increasing thermal stability toward that of its unbound counterpart. This study thus identifies a sorption threshold below which NOM sorption to goethite decreases NOM thermal stability, and above which no strong effects are manifested. This should likely influence the fate of organic carbon exposed to thermal gradients in natural environments.

Preferential adsorption of fluorescing fulvic and humic acid components on activated carbon using flow field-flow fractionation analysis.

PubMed

Schmit, Kathryn H; Wells, Martha J M

2002-02-01

Activated carbon treatment of drinking water is used to remove natural organic matter (NOM) precursors that lead to the formation of disinfection byproducts. The innate hydrophobic nature and macromolecular size of NOM render it amenable to sorption by activated carbon. Batch equilibrium and minicolumn breakthrough adsorption studies were performed using granular activated carbon to treat NOM-contaminated water. Ultraviolet (UV) absorption spectroscopy and flow field-flow fractionation analysis using tandem diode-array and fluorescence detectors were used to monitor the activated carbon sorption of NOM. Using these techniques, it was possible to study activated carbon adsorption properties of UV absorbing, fluorescing and nonfluorescing, polyelectrolytic macromolecules fractionated from the total macromolecular and nonmacromolecular composition of NOM. Adsorption isotherms were constructed at pH 6 and pH 9. Data were described by the traditional and modified Freundlich models. Activated carbon capacity and adsorbability were compared among fractionated molecular subsets of fulvic and humic acids. Preferential adsorption (or adsorptive fractionation) of polyelectrolytic, fluorescing fulvic and humic macromolecules on activated carbon was observed. The significance of observing preferential adsorption on activated carbon of fluorescing macromolecular components relative to nonfluorescing components is that this phenomenon changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the composition that existed in the aqueous phase prior to adsorption. Likewise, it changes the composition of dissolved organic matter remaining in equilibrium in the aqueous phase relative to the adsorbed phase. This research increases our understanding of NOM interactions with activated carbon which may lead to improved methods of potable water production.

Linear free energy relationships for the adsorption of volatile organic compounds onto multiwalled carbon nanotubes at different relative humidities: comparison with organoclays and activated carbon.

PubMed

Li, Mei-Syue; Wang, Reuben; Fu Kuo, Dave Ta; Shih, Yang-Hsin

2017-03-22

Accurate prediction of the sorption coefficients of volatile organic compounds (VOCs) on carbon nanotubes (CNTs) is of major importance for developing an effective VOC removal process and risk assessment of released nanomaterial-carrying contaminants. The linear free energy relationship (LFER) approach was applied to investigate the adsorption mechanisms of VOCs on multiwalled CNTs (MWCNTs). The gas-solid partition coefficients (log K d ) of 17 VOCs were determined at 0%, 55%, and 90% relative humidity (RH). The cavity/dispersion interaction is generally the most influential adsorption mechanism for all RH cases. The hydrogen-accepting interactions declined but with constant hydrogen-donating interactions during the increase of RH, suggesting that the acidity of VOC was important in forming sorptive interaction with the MWCNT surface. Moreover, the comparison of log K d of VOCs on MWCNTs and other sorbents revealed that the sorption performance of MWCNTs is much more stable over a wider range of RHs due to better site availability and site quality. Furthermore, for all 6 adsorbents in all RHs, the positive contribution of hydrogen bonding ability was found as compared to the negative one found for sorbents completely in water, indicating that the hydrogen-bond donor and acceptor on the sorbent surface contribute to the sorption in the gas phase. In conclusion, the LFER-derived coefficients can be useful in predicting the performance of VOC adsorption on adsorbents and in facilitating the design of efficient VOC removal systems.

Interaction of gases with ablative composites. II - Water

NASA Technical Reports Server (NTRS)

Honeycutt, R. H., III; Wightman, J. P.

1974-01-01

An investigation was conducted to study the sorption of water on two ablative composites and their components as a function of pressure and temperature. A pressure range from 0.001 to 10 torr and a temperature range from 25 to 35 C were considered in the investigation. It was found that the sorption of water vapor by the ablative composites and their components varied directly with pressure. The components of the ablative composites included phenolic spheres, cork, a carbon-glass fiber mixture, glass spheres, silica fibers, and a silicone elastomer.

Temperature-pressure conditions in coalbed methane reservoirs of the Black Warrior basin: Implications for carbon sequestration and enhanced coalbed methane recovery

USGS Publications Warehouse

Pashin, J.C.; McIntyre, M.R.

2003-01-01

Sorption of gas onto coal is sensitive to pressure and temperature, and carbon dioxide can be a potentially volatile supercritical fluid in coalbed methane reservoirs. More than 5000 wells have been drilled in the coalbed methane fields of the Black Warrior basin in west-central Alabama, and the hydrologic and geothermic information from geophysical well logs provides a robust database that can be used to assess the potential for carbon sequestration in coal-bearing strata.Reservoir temperature within the coalbed methane target zone generally ranges from 80 to 125 ??F (27-52 ??C), and geothermal gradient ranges from 6.0 to 19.9 ??F/1000 ft (10.9-36.2 ??C/km). Geothermal gradient data have a strong central tendency about a mean of 9.0 ??F/1000 ft (16.4 ??C/km). Hydrostatic pressure gradients in the coalbed methane fields range from normal (0.43 psi/ft) to extremely underpressured (<0.05 psi/ft). Pressure-depth plots establish a bimodal regime in which 70% of the wells have pressure gradients greater than 0.30 psi/ft, and 20% have pressure gradients lower than 0.10 psi/ft. Pockets of underpressure are developed around deep longwall coal mines and in areas distal to the main hydrologic recharge zone, which is developed in structurally upturned strata along the southeastern margin of the basin.Geothermal gradients within the coalbed methane fields are high enough that reservoirs never cross the gas-liquid condensation line for carbon dioxide. However, reservoirs have potential for supercritical fluid conditions beyond a depth of 2480 ft (756 m) under normally pressured conditions. All target coal beds are subcritically pressured in the northeastern half of the coalbed methane exploration fairway, whereas those same beds were in the supercritical phase window prior to gas production in the southwestern half of the fairway. Although mature reservoirs are dewatered and thus are in the carbon dioxide gas window, supercritical conditions may develop as reservoirs equilibrate toward a normal hydrostatic pressure gradient after abandonment. Coal can hold large quantities of carbon dioxide under supercritical conditions, and supercritical isotherms indicate non-Langmiur conditions under which some carbon dioxide may remain mobile in coal or may react with formation fluids or minerals. Hence, carbon sequestration and enhanced coalbed methane recovery show great promise in subcritical reservoirs, and additional research is required to assess the behavior of carbon dioxide in coal under supercritical conditions where additional sequestration capacity may exist. ?? 2003 Elsevier Science B.V. All rights reserved.

Characteristics of and sorption to biochars derived from waste material

NASA Astrophysics Data System (ADS)

Sun, Huichao; Kah, Melanie; Sigmund, Gabriel; Hofmann, Thilo

2015-04-01

Biochars can exhibit a high sorption potential towards heavy metals and organic contaminants in various environmental matrices (e.g., water, soil). They have therefore been proposed for environmental remediation purposes to sequester contaminants. To date, most studies have focused on the physicochemical and sorption properties of mineral phases poor biochars, which are typically produced from plant residues. Only little knowledge is available for biochars derived from human and animal waste material, which are typically characterized by high mineral contents (e.g., sewage sludge, manure). Using human and animal waste as source material to produce biochars would support the development of attractive combined strategies for waste management and remediation. The potential impact of mineral phases on the physicochemical and sorption properties of biochars requires further studies so that the potential as sorbent material can be evaluated. With this purpose, different source material biochars were produced at 200°C, 350°C and 500°C, to yield a series of biochars representing a range of mineral content. The derived biochars from wood shavings (<1% ash), sewage sludge (50-70% ash) and pig manure (30-60% ash), as well as a commercial biochar derived from grain husks (40% ash), were extensively characterized (e.g., element composition, surface area, porosity, Fourier transform infrared spectroscopy). The contents of potentially toxic elements (i.e., heavy metals and polycyclic aromatic hydrocarbons) of all materials were within the guidelines values proposed by the International Biochar Initiative, indicating their suitability for environmental application. Single point sorption coefficients for the model sorbate pyrene were measured to investigate the effect of mineral content, feedstock, pyrolysis temperature, particle size fractions and acid demineralization on sorption behavior. Overall, sorption of pyrene was strong for all materials (4 < Log Kd < 6.5 L/kg). Sorption generally increased with increasing pyrolysis temperature but there was no effect of particle size on sorption affinity. For mineral phase rich biochars, sorption generally increased after acid demineralization. When considering all materials together, the sorbent aromaticity (hydrogen-carbon ratio) was the most important factor controlling sorption of pyrene. Overall, the study demonstrates that biochars derived from human and animal waste material and exhibiting high mineral contents have potential for remediation applications.

Monohydrocalcite: a promising remediation material for hazardous anions

PubMed Central

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-01-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite. PMID:27877452

Monohydrocalcite: a promising remediation material for hazardous anions.

PubMed

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-12-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO 3 ·H 2 O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO 4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO 4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO 4 than calcite and aragonite. The modes of PO 4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite.

Monohydrocalcite: a promising remediation material for hazardous anions

NASA Astrophysics Data System (ADS)

Fukushi, Keisuke; Munemoto, Takashi; Sakai, Minoru; Yagi, Shintaro

2011-12-01

The formation conditions, solubility and stability of monohydrocalcite (MHC, CaCO3·H2O), as well as sorption behaviors of toxic anions on MHC, are reviewed to evaluate MHC as a remediation material for hazardous oxyanions. MHC is a rare mineral in geological settings that occurs in recent sediments in saline lakes. Water temperature does not seem to be an important factor for MHC formation. The pH of lake water is usually higher than 8 and the Mg/Ca ratio exceeds 4. MHC synthesis experiments as a function of time indicate that MHC is formed from amorphous calcium carbonate and transforms to calcite and/or aragonite. Most studies show that MHC forms from solutions containing Mg, which inhibits the formation of stable calcium carbonates. The solubility of MHC is higher than those of calcite, aragonite and vaterite, but lower than those of ikaite and amorphous calcium carbonate at ambient temperature. The solubility of MHC decreases with temperature. MHC is unstable and readily transforms to calcite or aragonite. The transformation consists of the dissolution of MHC and the subsequent formation of stable phases from the solution. The rate-limiting steps of the transformation of MHC are the nucleation and growth of stable crystalline phases. Natural occurrences indicate that certain additives, particularly PO4 and Mg, stabilize MHC. Laboratory studies confirm that a small amount of PO4 in solution (>30 μM) can significantly inhibit the transformation of MHC. MHC has a higher sorption capacity for PO4 than calcite and aragonite. The modes of PO4 uptake are adsorption on the MHC surface at moderate phosphate concentrations and precipitation of secondary calcium phosphate minerals at higher concentrations. Arsenate is most likely removed from the solution during the transformation of MHC. The proposed sorption mechanism of arsenate is coprecipitation during crystallization of aragonite. The arsenic sorption capacity by MHC is significantly higher than simple adsorption on calcite.

Structure of nanoporous carbon materials for supercapacitors

NASA Astrophysics Data System (ADS)

Volperts, A.; Mironova-Ulmane, N.; Sildos, I.; Vervikishko, D.; Shkolnikov, E.; Dobele, G.

2012-08-01

Activated carbons with highly developed porous structure and nanosized pores (8 - 11 Å) were prepared from alder wood using thermochemical activation method with sodium hydroxide. Properties of the obtained activated carbons were examined by benzene and nitrogen sorption, X-Ray diffraction and Raman spectroscopy. Tests of activated carbons as electrodes in supercapacitors were performed as well. It was found that specific surface area of above mentioned activated carbons was 1800 m2/g (Dubinin - Radushkevich). Raman spectroscopy demonstrated the presence of ordered and disordered structures of graphite origin. The performance of activated carbons as electrodes in supercapacitors have shown superior results in comparison with electrodes made with commercial carbon tissues.

Silicone passive equilibrium samplers as 'chemometers' in eels and sediments of a Swedish lake.

PubMed

Jahnke, Annika; Mayer, Philipp; McLachlan, Michael S; Wickström, Håkan; Gilbert, Dorothea; MacLeod, Matthew

2014-03-01

Passive equilibrium samplers deployed in two or more media of a system and allowed to come to equilibrium can be viewed as 'chemometers' that reflect the difference in chemical activities of contaminants between the media. We applied silicone-based equilibrium samplers to measure relative chemical activities of seven 'indicator' polychlorinated biphenyls (PCBs) and hexachlorobenzene in eels and sediments from a Swedish lake. Chemical concentrations in eels and sediments were also measured using exhaustive extraction methods. Lipid-normalized concentrations in eels were higher than organic carbon-normalized concentrations in sediments, with biota-sediment accumulation factors (BSAFs) of five PCBs ranging from 2.7 to 12.7. In contrast, chemical activities of the same pollutants inferred by passive sampling were 3.5 to 31.3 times lower in eels than in sediments. The apparent contradiction between BSAFs and activity ratios is consistent with the sorptive capacity of lipids exceeding that of sediment organic carbon from this ecosystem by up to 50-fold. Factors that may contribute to the elevated activity in sediments are discussed, including slower response of sediments than water to reduced emissions, sediment diagenesis and sorption to phytoplankton. The 'chemometer' approach has the potential to become a powerful tool to study the thermodynamic controls on persistent organic chemicals in the environment and should be extended to other environmental compartments.

Cadmium Sorption Characteristics of Soil Amendments and its Relationship with the Cadmium Uptake by Hyperaccumulator and Normal Plants in Amended Soils

PubMed Central

Sun, Yan; Wu, Qi-Tang; Lee, Charles C.C.; Li, Baoqin; Long, Xinxian

2013-01-01

In order to select appropriate amendments for cropping hyperaccumulator or normal plants on contaminated soils and establish the relationship between Cd sorption characteristics of soil amendments and their capacity to reduce Cd uptake by plants, batch sorption experiments with 11 different clay minerals and organic materials and a pot experiment with the same amendments were carried out. The pot experiment was conducted with Sedum alfredii and maize (Zea mays) in a co-cropping system. The results showed that the highest sorption amount was by montmorillonite at 40.82 mg/g, while mica was the lowest at only 1.83 mg/g. There was a significant negative correlation between the n value of Freundlich equation and Cd uptake by plants, and between the logarithm of the stability constant K of the Langmuir equation and plant uptake. Humic acids (HAs) and mushroom manure increased Cd uptake by S. alfredii, but not maize, thus they are suitable as soil amendments for the co-cropping S. alfredii and maize. The stability constant K in these cases was 0.14–0.16 L/mg and n values were 1.51–2.19. The alkaline zeolite and mica had the best fixation abilities and significantly decreased Cd uptake by the both plants, with K ≥ 1.49 L/mg and n ≥ 3.59. PMID:24912231

Acid sorption regeneration process using carbon dioxide

DOEpatents

King, C. Judson; Husson, Scott M.

2001-01-01

Carboxylic acids are sorbed from aqueous feedstocks onto a solid adsorbent in the presence of carbon dioxide under pressure. The acids are freed from the sorbent phase by a suitable regeneration method, one of which is treating them with an organic alkylamine solution thus forming an alkylamine-carboxylic acid complex which thermally decomposes to the desired carboxylic acid and the alkylamine.

Single and competitive adsorption of OMPs by carbon nanotubes - mechanism and fitting models

NASA Astrophysics Data System (ADS)

Kamińska, Gabriela; Dudziak, Mariusz; Bohdziewicz, Jolanta; Kudlek, Edyta

2017-11-01

The adsorption of three organic micropollutants (diclofenac - DFN, pentachlorophenol - PCP and octylphenol - OP) on two kinds of carbon nanotubes (single walled carbon nanotubes - SWCNT and single walled carbon nanotubes with amine group - SWCNT-NH2) was investigated, in single and bicomponent solution at pH 5. SWCNT-NH2 had three times lower specific surface area than SWCNT. Significant differences were observed in sorption capacity of SWCNT and SWCNT-NH2 for given chemicals. The sorption uptake changes in the following order: OP > PCP > DFN for SWCNT and DFN > PCP > OP for SWCNT-NH2. A few times higher adsorption of OP on SWCNT came from low OP solubility in water in comparison to PCP and DFN. While, higher adsorption of DFN and PCP on SWCNT-NH2 was a result of electrostatic attraction between dissociated form of these chemicals and positively charged SWCNT-NH2 at pH 5. In adsorption from bicomponent solution, significant competition was observed between PCP and DFN due to similar adsorption mechanism on SWCNT-NH2. Opposite tendency was observed for SWCNT, DFN did not greatly affect adsorption of PCP and OP since they were very easily absorbable by sigma-sigma interaction.

Sorption and desorption of organophosphate esters with different hydrophobicity by soils.

PubMed

Cristale, Joyce; Álvarez-Martín, Alba; Rodríguez-Cruz, Sonia; Sánchez-Martín, María J; Lacorte, Silvia

2017-12-01

Organophosphate esters (OPEs) are ubiquitous contaminants with potentially hazardous effects on both the environment and human health. Knowledge about the soil sorption-desorption process of organic chemicals is important in order to understand their fate, mobility, and bioavailability, enabling an estimation to be made of possible risks to the environment and biota. The aim of this study was to use the batch equilibrium technique to evaluate the sorption-desorption behavior of seven OPEs (TCEP, TCPP, TBEP, TDCP, TBP, TPhP, and EHDP) in soils with distinctive characteristics (two unamended soils and a soil amended with sewage sludge). The equilibrium concentrations of the OPEs were determined by high performance liquid chromatography coupled to a triple quadrupole mass spectrometer (HPLC-MS/MS). All the compounds were sorbed by the soils, and soil organic carbon (OC) played an important role in this process. The sorption of the most soluble OPEs (TCEP, TCPP, and TBEP) depended on soil OC content, although desorption was ≥ 58.1%. The less water-soluble OPEs (TDCP, TBP, TPhP, and EHDP) recorded total sorption (100% for TPhP and EHDP) or very high sorption (≥ 34.9%) by all the soils and were not desorbed, which could be explained by their highly hydrophobic nature, as indicated by the logarithmic octanol/water partition coefficient (K ow ) values higher than 3.8, resulting in a high affinity for soil OC. The results of the sorption-desorption of the OPEs by soils with different characteristics highlighted the influence of these compounds' physicochemical properties and the content and nature of soil OC in this process.

Geochemistry and migration of contaminants at the Weldon Spring chemical plant site, St. Charles County, Missouri, 1989-91

USGS Publications Warehouse

Schumacher, John G.

1993-01-01

The geochemistry of the shallow aquifer and geochemical controls on the migration of uranium and other constituents from raffinate pits were determined at the Weldon Spring chemical plant site. Surface-water samples from the raffinate pits con- tained large concentrations of calcium, magnesium, sodium, potassium, sulfate, nitrite, lithium, moly- bdenum, strontium, vanadium, and uranium. Analyses of interstitial-water samples from raffinate pit 3 indicated that concentrations of most constituents increased with increasing depth below the water- sediment interface. Nitrate and uranium were not chemically reduced and attenuated within the raffinate pits and can be expected to migrate into the overburden. Laboratory sorption experiments were performed to evaluate the effect of pH value on the sorption of several raffinate constituents by the overburden. No sorption of calcium, sodium, sulfate, nitrate, or lithium was observed. Sorption of molybdenum was dependent on solution pH and sorption of uranium was dependent on solution pH and carbonate concentration. The sorption of uranium and molybdenum was consistent with sorption controlled by oxyhydroxides. The quality of water collected in overburden lysimeters near raffinate pit 4 can be modeled as a mixture of water from raffinate pits 3 and 4, and an uncontaminated com- ponent in a system at equilibrium with ferrihydrite and calcite. Increased constituent concentrations in a perennial spring north of the site were the result of a subsurface connection between the spring and several losing stream segments receiving runoff from the site, in addition to seepage from the raffinate pits.

Use of Pyrogenic Carbon Geosorbents to Decrease the Mobility and Bioavailability of Pharmaceuticals in the Soil-Water-Biota Continuum

NASA Astrophysics Data System (ADS)

Liu, Cheng-Hua; Zhang, Yingjie; Bhalsod, Gemini; Chuang, Ya-Hui; Boyd, Stephen; Teppen, Brian; Tiedje, James; Li, Hui; Zhang, Wei

2016-04-01

Pharmaceuticals are emerging contaminants widely detected in soil and water environments, and concerns are mounting over their potential impact on human and ecosystem health. In particular, overuse of antibiotics (an important group of pharmaceuticals) in human medicine and animal agriculture and rapid emergence of antibiotic resistant bacteria on a global scale are threatening the health of humans, animals, and the environment. We have investigated interactions of pharmaceuticals with pyrogenic carbon geosorbents (e.g., biohar and activated carbon), bacteria, and vegetable crops in order to better understand sorption, uptake, and translocation of pharmaceuticals in the soil-water-biota continuum. Sorption of antibiotics by biochars was studied to assess the effect of biochar soil amendment in reducing the transport and bioavailability of antibiotics. Pyrogenic carbonaceous materials such as biochars and activated carbon had strong sorption capacities for antibiotics, and drastically lowed the uptake of antibiotics by an Escherichia coli, therefore demonstrating soil amendment with pyrogenic carbon geosorbents as an effective remediation strategy to reduce antibiotic transport and selection pressure for antibiotic resistant bacteria. Additionally, because consuming pharmaceutical-tainted food is a direct human exposure pathway, it is critical to investigate the residue levels of pharmaceuticals in food crops grown in contaminated soils or irrigated with reclaimed water. Therefore, we have studied the uptake and accumulations of pharmaceuticals in greenhouse-grown lettuce under overhead or surface irrigations. Preliminary results indicate that pharmaceuticals of large molecular weight and low water solubility had greater concentrations in lettuce shoots under overhead irrigation than surface irrigation. Pharmaceuticals of low molecular weight and high water solubility are less clearly influenced by irrigation methods. These results implies that irrigation scheme needs to be optimized when using the reclaimed water for crop irrigation. In summary, scientifically-sound soil and water management practices are needed to minimize the transfer of pharmaceuticals from soil and water to crops and microorganisms.

Sorption and stability of the polycyclic nitramine explosive CL-20 in soil.

PubMed

Balakrishnan, Vimal K; Monteil-Rivera, Fanny; Gautier, Mathieu A; Hawari, Jalal

2004-01-01

The polycyclic nitramine CL-20 (2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane) is being considered for use as a munition, but its environmental fate and impact are unknown. The present study consisted of two main elements. First, sorption-desorption data were measured with soils and minerals to evaluate the respective contributions of organic matter and minerals to CL-20 immobilization. Second, since CL-20 hydrolyzes at a pH of >7, the effect of sorption on CL-20 degradation was examined in alkaline soils. Sorption-desorption isotherms measured using five slightly acidic soils (5.1 < pH < 6.9) containing various amounts of total organic carbon (TOC) revealed a nonlinear sorption that increased with TOC [K(d) (0.33% TOC) = 2.4 L kg(-1); K(d) (20% TOC) = 311 L kg(-1)]. Sorption to minerals (Fe(2)O(3), silica, kaolinite, montmorillonite, illite) was very low (0 < K(d) < 0.6 L kg(-1)), suggesting that mineral phases do not contribute significantly to CL-20 sorption. Degradation of CL-20 in sterile soils having different pH values increased as follows: sandy agricultural topsoil from Varennes, QC, Canada (VT) (pH = 5.6; K(d) = 15 L kg(-1); 8% loss) < clay soil from St. Sulpice, QC, Canada (CSS) (pH = 8.1; K(d) = 1 L kg(-1); 82% loss) < sandy soil provided by Agriculture Canada (SAC) (pH = 8.1, K(d) = approximately 0 L kg(-1); 100% loss). The faster degradation in SAC soil compared with CSS soil was attributed to the absence of sorption in the former. In summary, CL-20 is highly immobilized by soils rich in organic matter. Although sorption retards abiotic degradation, CL-20 still decomposes in soils where pH is >7.5, suggesting that it will not persist in even slightly alkaline soils.

Adsorption with Biochar or Activated Carbon as Treatment Processes for Greywater Reuse

NASA Astrophysics Data System (ADS)

Thompson, K.; Cook, S. M.; Summers, R. S.

2017-12-01

Nearly 3 billion people experience water scarcity in their watershed for at least one month every year. Population growth, urbanization, and global climate change are increasing the severity of water scarcity in many areas. Decentralized reuse of greywater from showers, baths, and bathroom sinks could reduce residential water demand by 35% and urban water demand by 15%. Decentralized greywater reuse could be environmentally sustainable due to less energy for pumping than centralized systems. However, decentralized greywater reuse presents challenges from economies of scale. Biochar can serve as a low-cost, environmentally sustainable alternative to activated carbon (AC) in water treatment. Many studies have explored biochar as a sorbent for surface water or wastewater, but studies about biochar for greywater treatment are limited. The objectives of this study were (1) to compare the performance of biochar and AC for sorption of dissolved organic carbon (DOC) in greywater and (2) to determine whether AC or biochar can satisfy greywater treatment regulations alone or in combination with other processes. Jar tests with doses ranges of 0.25 to 4 g/L were used to compare sorbents for DOC removal after various pretreatments. All sorbents were ground to ≤45 µm particle diameter. Five biochars were screened to select the most effective greywater sorbent. These biochars covered a range of production temperatures, feedstocks, and lab- and full-scale production. Wood-based forced draft top lit updraft biochar (FD-TLUD) biochar was found to be the most effective for DOC removal from both real and synthetic greywater. Sorption with FD-TLUD biochar or AC can remove up to 70% or 80% of DOC from greywater, respectively. AC sorption of DOC was only 1-10% greater at each dose from a greywater sample with 11 mg/L DOC than from a greywater sample with 43 mg/L DOC. Coagulation with 30 mg/L alum removed 14% of greywater DOC, and biochar or AC sorption removed similar percentages of DOC from microfiltered or coagulated greywater. UVA254 removal correlated strongly with DOC removal for both AC and biochar (R2=0.89). These results indicate that biochar could be useful component in greywater treatment systems. Future work will focus on sorption after other chemical and biological pretreatments.

Evaluation of magnetic- and carbon-based nano-adsorbents application in pre-purification of paclitaxel from needles of Taxus baccata

NASA Astrophysics Data System (ADS)

Naghavi, M. R.; Motamedi, E.; Nasiri, J.; Alizadeh, H.; Fattahi Moghadam, M. R.; Mashouf, A.

2015-01-01

In this investigation, the proficiency of a number of magnetic carbon-based nano-adsorbents is evaluated in pre-purification process of the crude paclitaxel extract obtained from fresh needles of yew tree ( Taxus baccata L.). The effectiveness and removal ability of color and impurities from crude extracts, for three novel candidate nano-adsorbents (i.e., Fe3O4 nanoparticles (Fe3O4Nps), graphite oxide (GO), and their hybrids Fe3O4Nps/GO) are compared with commercial graphite in three different solvents. In general, both HPLC and UV-Vis spectroscopy results demonstrate that in less polar solvent (i.e., dichloromethane), the adsorption is greatly affected by the electrostatic attractions, while in more polar solvents (i.e., acetone and ethanol) π-π electron interactions taking place between adsorbent and adsorbate are the most dominant factors in sorption. Considering decolorization efficiency, purity of taxol, recovery and reusability of adsorbents, Fe3O4Nps/GO (50 g/L) in dichloromethane is selected as the best medium for pre-purification of paclitaxel. Additionally, in kinetic studies the sorption equilibrium can be reached within 120 min, and the experimental data are well fitted by the pseudo-second-order model. The Langmuir sorption isotherm model correlates well with the sorption equilibrium data for the crude extract concentration (500-2,000 mg/L). Our findings display promising applications of Fe3O4Nps/GO, as a cost-effective nano-adsorbent, to provide a suitable vehicle toward improvement of paclitaxel pre-purification.

Modeling the production, decomposition, and transport of dissolved organic carbon in boreal soils

USGS Publications Warehouse

Fan, Zhaosheng; Neff, Jason C.; Wickland, Kimberly P.

2010-01-01

The movement of dissolved organic carbon (DOC) through boreal ecosystems has drawn increased attention because of its potential impact on the feedback of OC stocks to global environmental change in this region. Few models of boreal DOC exist. Here we present a one-dimensional model with simultaneous production, decomposition, sorption/desorption, and transport of DOC to describe the behavior of DOC in the OC layers above the mineral soils. The field-observed concentration profiles of DOC in two moderately well-drained black spruce forest sites (one with permafrost and one without permafrost), coupled with hourly measured soil temperature and moisture, were used to inversely estimate the unknown parameters associated with the sorption/desorption kinetics using a global optimization strategy. The model, along with the estimated parameters, reasonably reproduces the concentration profiles of DOC and highlights some important potential controls over DOC production and cycling in boreal settings. The values of estimated parameters suggest that humic OC has a larger potential production capacity for DOC than fine OC, and most of the DOC produced from fine OC was associated with instantaneous sorption/desorption whereas most of the DOC produced from humic OC was associated with time-dependent sorption/desorption. The simulated DOC efflux at the bottom of soil OC layers was highly dependent on the component and structure of the OC layers. The DOC efflux was controlled by advection at the site with no humic OC and moist conditions and controlled by diffusion at the site with the presence of humic OC and dry conditions.

Influence of low oxygen tensions and sorption to sediment black carbon on biodegradation of pyrene.

PubMed

Ortega-Calvo, José-Julio; Gschwend, Philip M

2010-07-01

Sorption to sediment black carbon (BC) may limit the aerobic biodegradation of polycyclic aromatic hydrocarbons (PAHs) in resuspension events and intact sediment beds. We examined this hypothesis experimentally under conditions that were realistic in terms of oxygen concentrations and BC content. A new method, based on synchronous fluorescence observations of (14)C-pyrene, was developed for continuously measuring the uptake of dissolved pyrene by Mycobacterium gilvum VM552, a representative degrader of PAHs. The effect of oxygen and pyrene concentrations on pyrene uptake followed Michaelis-Menten kinetics, resulting in a dissolved oxygen half-saturation constant (K(om)) of 14.1 microM and a dissolved pyrene half-saturation constant (K(pm)) of 6 nM. The fluorescence of (14)C-pyrene in air-saturated suspensions of sediments and induced cells followed time courses that reflected simultaneous desorption and biodegradation of pyrene, ultimately causing a quasi-steady-state concentration of dissolved pyrene balancing desorptive inputs and biodegradation removals. The increasing concentrations of (14)CO(2) in these suspensions, as determined with liquid scintillation, evidenced the strong impact of sorption to BC-rich sediments on the biodegradation rate. Using the best-fit parameter values, we integrated oxygen and sorption effects and showed that oxygen tensions far below saturation levels in water are sufficient to enable significant decreases in the steady-state concentrations of aqueous-phase pyrene. These findings may be relevant for bioaccumulation scenarios that consider the effect of sediment resuspension events on exposure to water column and sediment pore water, as well as the direct uptake of PAHs from sediments.

Sorption of pollutants by porous carbon, carbon nanotubes and fullerene- an overview.

PubMed

Gupta, Vinod K; Saleh, Tawfik A

2013-05-01

The quality of water is continuously deteriorating due to its increasing toxic threat to humans and the environment. It is imperative to perform treatment of wastewater in order to remove pollutants and to get good quality water. Carbon materials like porous carbon, carbon nanotubes and fullerene have been extensively used for advanced treatment of wastewaters. In recent years, carbon nanomaterials have become promising adsorbents for water treatment. This review attempts to compile relevant knowledge about the adsorption activities of porous carbon, carbon nanotubes and fullerene related to various organic and inorganic pollutants from aqueous solutions. A detailed description of the preparation and treatment methods of porous carbon, carbon nanotubes and fullerene along with relevant applications and regeneration is also included.

Design and development of a four-cell sorption compressor based J-T cooler using R134a as working fluid

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mehta, R. N.; Bapat, S. L.; Atrey, M. D.

The need of a cooler with no electromagnetic interference and practically zero vibration has led to sorption compressor based Joule-Thomson (J-T) coolers. These are useful for sophisticated electronic, ground based and space borne systems. In a Sorption compressor, adsorbed gases are desorbed into a confined volume by raising temperature of the sorption bed resulting in an increase in pressure of the liberated gas. In order to have the system (compressor) functioning on a continuous basis, with almost a constant gas flow rate, multiple cells are used with the adaptation of Temperature Swing Adsorption (TSA) process. As the mass of themore » desorbed gas dictates the compressor throughput, a combination of sorbent material with high adsorption capacity for a chosen gas or gas mixture has to be selected for efficient operation of the compressor. Commercially available (coconut-shell base) activated carbon has been selected for the present application. The characterization study for variation of discharge pressure is used to design the Four-cell sorption compressor based cryocooler with a desired output. Apart from compressor, the system includes a) After cooler b) Return gas heat exchanger c) capillary tube as the J-T expansion device and d) Evaporator.« less

Design and development of a four-cell sorption compressor based J-T cooler using R134a as working fluid

NASA Astrophysics Data System (ADS)

Mehta, R. N.; Bapat, S. L.; Atrey, M. D.

2014-01-01

The need of a cooler with no electromagnetic interference and practically zero vibration has led to sorption compressor based Joule-Thomson (J-T) coolers. These are useful for sophisticated electronic, ground based and space borne systems. In a Sorption compressor, adsorbed gases are desorbed into a confined volume by raising temperature of the sorption bed resulting in an increase in pressure of the liberated gas. In order to have the system (compressor) functioning on a continuous basis, with almost a constant gas flow rate, multiple cells are used with the adaptation of Temperature Swing Adsorption (TSA) process. As the mass of the desorbed gas dictates the compressor throughput, a combination of sorbent material with high adsorption capacity for a chosen gas or gas mixture has to be selected for efficient operation of the compressor. Commercially available (coconut-shell base) activated carbon has been selected for the present application. The characterization study for variation of discharge pressure is used to design the Four-cell sorption compressor based cryocooler with a desired output. Apart from compressor, the system includes a) After cooler b) Return gas heat exchanger c) capillary tube as the J-T expansion device and d) Evaporator.

Sorption and degradation of neonicotinoid insecticides in tropical soils.

PubMed

Dankyi, Enock; Gordon, Chris; Carboo, Derick; Apalangya, Vitus A; Fomsgaard, Inge S

2018-05-22

Neonicotinoids are the most widely applied class of insecticides in cocoa farming in Ghana. Despite the intensive application of these insecticides, knowledge of their fate in the Ghanaian and sub-Saharan African environment remains low. This study examined the behavior of neonicotinoids in soils from cocoa plantations in Ghana by estimating their sorption and degradation using established kinetic models and isotherms. Studies of sorption were conducted using the batch equilibrium method on imidacloprid, thiamethoxam, clothianidin, acetamiprid and thiacloprid, while degradation of imidacloprid, thiamethoxam and their respective deuterated counterparts was studied using models proposed by the European forum for coordination of pesticide fate and their use (FOCUS). Analytes were extracted using the quick, easy, cheap, effective, rugged and safe (QuEChERS) procedure and quantified by liquid chromatography-tandem mass spectrometry (LC-MS/MS). Average recoveries were high (≥ 85%) for all analytes. The findings from the study suggest that neonicotinoid insecticides may be persistent in the soils studied based on estimated half-lives > 150 days. The study also revealed generally low-sorption coefficients for neonicotinoids in soils, largely influenced by soil organic carbon.

Synthesis of 3D iron and carbon-based composite as a bifunctional sorbent and catalyst for remediation of organic pollutants

NASA Astrophysics Data System (ADS)

Li, Ling; Shen, Yi; Wang, Zhaomei

2017-07-01

We prepared a 3D monolith by integrating graphite nanosheet encapsulated iron nanoparticles (Fe@GNS) into graphite felt (GF) supports. The structural properties of the resulting Fe@GNS/GF monolith are characterized by x-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, x-ray photoelectron spectroscopy and N2 adsorption-desorption isotherms. The Fe@GNS/GF monoliths are utilized as a bifunctional sorbent and catalyst for water remediation. Using Congo red and methyl violet 2B as model pollutants, the sorption and catalytic performance of the Fe@GNS/GF composite are examined. The Fe@GNS/GF monolith possesses maximum sorption capacities of 177 and 142 mg g-1 for the sorption of CR and MV-2B, respectively. It also exhibits rate constants of 0.0563 and 0.0464 min-1 for the catalytic degradation of CR and MV-2B, respectively. As a proof of concept, the Fe@GNS/GF is successfully utilized to decontaminate simulated organic waste water via a combination of sorption and catalytic degradation processes.

Carbon dioxide capture utilizing zeolites synthesized with paper sludge and scrap-glass.

PubMed

Espejel-Ayala, F; Corella, R Chora; Pérez, A Morales; Pérez-Hernández, R; Ramírez-Zamora, R M

2014-12-01

The present work introduces the study of the CO2 capture process by zeolites synthesized from paper sludge and scrap glass. Zeolites ZSM-5, analcime and wairakite were produced by means of two types of Structure Directing Agents (SDA): tetrapropilamonium (TPA) and ethanol. On the one hand, zeolite ZSM-5 was synthesized using TPA; on the other hand, analcime and wairakite were produced with ethanol. The temperature programmed desorption (TPD) technique was performed for determining the CO2 sorption capacity of these zeolites at two sorption temperatures: 50 and 100 °C. CO2 sorption capacity of zeolite ZSM-5 synthesized at 50 °C was 0.683 mmol/g representing 38.2% of the value measured for a zeolite ZSM-5 commercial. Zeolite analcime showed a higher CO2 sorption capacity (1.698 mmol/g) at 50 °C and its regeneration temperature was relatively low. Zeolites synthesized in this study can be used in the purification of biogas and this will produce energy without increasing the atmospheric CO2 concentrations. © The Author(s) 2014.

Effects of reducing temperatures on the hydrogen storage capacity of double-walled carbon nanotubes with Pd loading.

PubMed

Sheng, Qu; Wu, Huimin; Wexler, David; Liu, Huakun

2014-06-01

The effects of different temperatures on the hydrogen sorption characteristics of double-walled carbon nanotubes (DWCNTs) with palladium loading have been investigated. When we use different temperatures, the particle sizes and specific surface areas of the samples are different, which affects the hydrogen storage capacity of the DWCNTs. In this work, the amount of hydrogen storage capacity was determined (by AMC Gas Reactor Controller) to be 1.70, 1.85, 2.00, and 1.93 wt% for pristine DWCNTS and for 2%Pd/DWCNTs-300 degrees C, 2%Pd/DWCNTs-400 degrees C, and 2%Pd/DWCNTs-500 degrees C, respectively. We found that the hydrogen storage capacity can be enhanced by loading with 2% Pd nanoparticles and selecting a suitable temperature. Furthermore, the sorption can be attributed to the chemical reaction between atomic hydrogen and the dangling bonds of the DWCNTs.

Development of Trace Contaminant Control Prototypes for the Primary Life Support System (PLSS)

NASA Technical Reports Server (NTRS)

Wojtowicz, Marek; Cosgrove, Joseph E.; Serio, Michael E.; Nalette, Tim; Guerrero, Sandra V.; Papale, William; Wilburn, Monique S.

2017-01-01

Results are presented on the development of Trace Contaminant Control (TCC) Prototypes for use in Extravehicular Activities (EVAs), and more specifically in the Primary Life Support System (PLSS). The current TC-control technology involves the use of a packed bed of acid-impregnated granular charcoal, which is non-regenerable, and the carbon-based sorbent under development in this project can be regenerated by exposure to vacuum at room temperature. Data on sorption and desorption of ammonia and formaldehyde, which are major TCs of concern, as well as pressure-drop calculations were used to design and test 1/6-scale and full-scale trace contaminant control system (TCCS) prototypes. Carbon sorbents were fabricated in both the granular and foam-supported forms. Sorbent performance was tested for ammonia sorption and vacuum regeneration in 1/6-scale, and pressure-drop characteristics were measured at flow rates relevant to the PLSS application.

EVALUATION OF CARBON DIOXIDE CAPTURE FROM EXISTING COAL FIRED PLANTS BY HYBRID SORPTION USING SOLID SORBENTS

DOE Office of Scientific and Technical Information (OSTI.GOV)

Benson, Steven; Palo, Daniel; Srinivasachar, Srivats

2014-12-01

Under contract DE-FE0007603, the University of North Dakota conducted the project Evaluation of Carbon Dioxide Capture from Existing Coal Fired Plants by Hybrid Sorption Using Solid Sorbents. As an important element of this effort, an Environmental Health and Safety (EH&S) Assessment was conducted by Barr Engineering Co. (Barr) in association with the University of North Dakota. The assessment addressed air and particulate emissions as well as solid and liquid waste streams. The magnitude of the emissions and waste streams was estimated for evaluation purposes. EH&S characteristics of materials used in the system are also described. This document contains data basedmore » on the mass balances from both the 40 kJ/mol CO2 and 80 kJ/mol CO2 desorption energy cases evaluated in the Final Technical and Economic Feasibility study also conducted by Barr Engineering.« less

Hydrogen Crystallization in Low-Density Aerogels

DOE PAGES

Kucheyev, S. O.; Van Cleve, E.; Johnston, L. T.; ...

2015-03-17

Crystallization of liquids confined in disordered low-density nanoporous scaffolds is poorly understood. Here in this work, we use relaxation calorimetry to study the liquid–solid phase transition of H 2 in a series of silica and carbon (nanotube- and graphene-based) aerogels with porosities ≳94%. Results show that freezing temperatures of H 2 inside all the aerogels studied are depressed but do not follow predictions of the Gibbs–Thomson theory based on average pore diameters measured by conventional gas sorption techniques. Instead, we find that, for each material family investigated, the depression of average freezing temperatures scales linearly with the ratio of themore » internal surface area (measured by gas sorption) and the total pore volume derived from the density of aerogel monoliths. The slope of such linear dependences is, however, different for silica and carbon aerogels, which we attribute to microporosity of carbons and the presence of macropores in silica aerogels. In conclusion, our results have important implications for the analysis of pore size distributions of low-density nanoporous materials and for controlling crystallization of fuel layers in targets for thermonuclear fusion energy applications.« less

Use of sorption technology for treatment of humidity condensate for potable water

NASA Technical Reports Server (NTRS)

Ajjarapu, Sundara R. M.; Symons, J. M.

1992-01-01

This research focused on the testing of the original potable water processor aboard Space Station Freedom that was to produce potable water from the humidity condensate and additional water generated by carbon dioxide reduction. Humidity condensate was simulated by an influent water model 'Ersatz'. The humidity condensate was treated with multifiltration (MF) beds that consisted of a train of sorption beds (referred to as 'Unibed') designed to remove specific contaminants. For the complete simulated MF system runs tested for 100 bed volumes (BV) (volume processed/total column volume), 0.6 percent of the TOC was removed by the SAC/IRN 77 (Strong Acid Cation exchange resin), 39.6 percent of the total organic carbon (TOC) was removed by the WBA/IRA 68 (Weak Base Anion exchange resin), 13.2 percent of the TOC was removed by activated carbon adsorption (580-26), and the remaining sorbent media acted as polishing units to remove an additional 1.6 percent of the TOC at steady state. At steady state, 45 percent of the influent TOC passed through the MF bed.

Hydrogen crystallization in low-density aerogels.

PubMed

Kucheyev, S O; Van Cleve, E; Johnston, L T; Gammon, S A; Worsley, M A

2015-04-07

Crystallization of liquids confined in disordered low-density nanoporous scaffolds is poorly understood. Here, we use relaxation calorimetry to study the liquid-solid phase transition of H2 in a series of silica and carbon (nanotube- and graphene-based) aerogels with porosities ≳94%. Results show that freezing temperatures of H2 inside all the aerogels studied are depressed but do not follow predictions of the Gibbs-Thomson theory based on average pore diameters measured by conventional gas sorption techniques. Instead, we find that, for each material family investigated, the depression of average freezing temperatures scales linearly with the ratio of the internal surface area (measured by gas sorption) and the total pore volume derived from the density of aerogel monoliths. The slope of such linear dependences is, however, different for silica and carbon aerogels, which we attribute to microporosity of carbons and the presence of macropores in silica aerogels. Our results have important implications for the analysis of pore size distributions of low-density nanoporous materials and for controlling crystallization of fuel layers in targets for thermonuclear fusion energy applications.

Micropollutant sorption to membrane polymers: a review of mechanisms for estrogens.

PubMed

Schäfer, Andrea I; Akanyeti, Ime; Semião, Andrea J C

2011-05-11

Organic micropollutants such as estrogens occur in water in increasing quantities from predominantly anthropogenic sources. In water such micropollutants partition not only to surfaces such as membrane polymers but also to any other natural or treatment related surfaces. Such interactions are often observed as sorption in treatment processes and this phenomenon is exploited in activated carbon filtration, for example. Sorption is important for polymeric materials and this is used for the concentration of such micropollutants for analytical purposes in solid phase extraction. In membrane filtration the mechanism of micropollutant sorption is a relatively new discovery that was facilitated through new analytical techniques. This sorption plays an important role in micropollutant retention by membranes although mechanisms of interaction are to date not understood. This review is focused on sorption of estrogens on polymeric surfaces, specifically membrane polymers. Such sorption has been observed to a large extent with values of up to 1.2 ng/cm(2) measured. Sorption is dependent on the type of polymer, micropollutant characteristics, solution chemistry, membrane operating conditions as well as membrane morphology. Likely contributors to sorption are the surface roughness as well as the microporosity of such polymers. While retention-and/or reflection coefficient as well as solute to effective pore size ratio-controls the access of such micropollutants to the inner surface, pore size, porosity and thickness as well as morphology or shape of inner voids determines the available area for sorption. The interaction mechanisms are governed, most likely, by hydrophobic as well as solvation effects and interplay of molecular and supramolecular interactions such as hydrogen bonding, π-cation/anion interactions, π-π stacking, ion-dipole and dipole-dipole interactions, the extent of which is naturally dependent on micropollutant and polymer characteristics. Systematic investigations are required to identify and quantify both relative contributions and strength of such interactions and develop suitable surface characterisation tools. This is a difficult endeavour given the complexity of systems, the possibility of several interactions taking place simultaneously and the generally weaker forces involved. Copyright © 2010 Elsevier B.V. All rights reserved.

Efficiency of biochar produced from malt spent rootlets to remove mercury and dyes

NASA Astrophysics Data System (ADS)

Kamenidou, Charoula; Manariotis, Ioannis; Karapanagioti, Hrissi

2017-04-01

Considerable research effort has been focused on the production of biochar from carbon-rich biomass under oxygen-limited conditions as a mitigation measure for global warming once it is used as a soil amendment. Furthermore, the use of biochar as an added value product, such as sorbent or catalyst, is desirable and could be more profitable. Biochar is obtained from the incomplete combustion of carbon-rich biomass under oxygen-limited conditions. Various organic-rich wastes including wood chips, animal manure, and crop residues have been used for biochar production. The present study presents the findings of an experimental work, which investigated the use of biochar produced from malt spent rootlets (MSR), which is a beer production by-product, to remove Hg(II) and methylene blue (MB) from aqueous solutions. MSR was pyrolyzed at temperatures of 300, 400, 500, 600, 750, 850, and 900oC, under limited oxygen conditions. The increase of temperature resulted in significantly increased BET surface areas. The mercury sorption capacity was affected by pyrolysis temperature, and was increased by increasing the pyrolysis temperature. The maximum sorption capacity was 100-110 mg Hg(II)/g biochar at a temperature range of 750-850oC. The MB sorption capacity of biochar was also affected by pyrolysis temperature.

Combining sorption experiments and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS) to study the adsorption of propranolol onto environmental solid matrices - Influence of copper(II).

PubMed

Smith, Rose-Michelle; Sayen, Stéphanie; Nuns, Nicolas; Berrier, Elise; Guillon, Emmanuel

2018-05-23

The bioavailability of pharmaceuticals is governed by their sorption in soils/sediments, as the retention processes determine their concentration in surface- and ground-water. The adsorption of these contaminants can involve various solid components such as organic matter, clays and metallic oxides, and their distribution among these solid components depends on contaminant and solid properties. In this paper we studied the adsorption of the pharmaceutical propranolol - a beta-blocker - on eight different solids (six soils, one sediment and one kaolinite-based sample) by batch experiments. The influence of contact time, propranolol concentration and pH was considered, as well as the presence of copper(II). The investigated solids displayed a wide variability in terms of CEC (cationic exchange capacity) and organic carbon and carbonates contents. The influence of pH was negligible in the pH range from 5.5 to 8.6. The adsorbed amounts were greatly dependent on the solid and two groups of solids were evidenced: three soils of high CEC and organic carbon contents which retained high amounts of propranolol, and three soils, the sediment and the kaolinite-based sample (low CEC and organic carbon content) displaying a low adsorption capacity for the beta-blocker. A linear model enabling the determination of the sorption parameters K d and K oc was pertinent to describe the adsorption isotherms but the K oc values showed a great variability. It was shown that organic carbon content alone could not explain propranolol adsorption. The CEC value was identified as influent parameter and a simple empirical model was proposed to describe propranolol adsorption. At microscopic and molecular scales, ToF-SIMS experiments indicated (i) a decrease of potassium on the surface upon propranolol adsorption with a distribution of the beta-blocker similarly to alumino-silicates, iron and organic carbon on the surface confirming a cation exchange mechanism and (ii) the absence of degradation products and copper-propranolol complexes. Copyright © 2018. Published by Elsevier B.V.

Sorption of Fluorotelomer Sulfonates, Fluorotelomer Sulfonamido Betaines, and a Fluorotelomer Sulfonamido Amine in National Foam Aqueous Film-Forming Foam to Soil.

PubMed

Barzen-Hanson, Krista A; Davis, Shannon E; Kleber, Markus; Field, Jennifer A

2017-11-07

During fire-fighter training, equipment testing, and emergency responses with aqueous film-forming foams (AFFFs), milligrams per liter concentrations of anionic, zwitterionic, and cationic per- and polyfluoroalkyl substances (PFASs) enter the environment. Because the behavior of zwitterionic and cationic PFASs in the subsurface is unknown, batch sorption experiments were conducted using National Foam AFFF, which contains anionic fluorotelomer sulfonates (FtSs), zwitterionic fluorotelomer sulfonamido betaines (FtSaBs), and cationic 6:2 fluorotelomer sulfonamido amine (FtSaAm). Sorption of the FtSs, FtSaBs, and 6:2 FtSaAm to six soils with varying organic carbon, effective cation-exchange capacity, and anion-exchange capacity was evaluated to determine sorption mechanisms. Due to the poor recovery of the FtSaBs and 6:2 FtSaAm with published PFAS soil extraction methods, a new soil extraction method was developed to achieve good (90-100%) recoveries. The 6:2 FtSaAm was depleted from the aqueous phase in all but one soil, which is attributed to electrostatic and hydrophobic interactions. Sorption of the FtSs was driven by hydrophobic interactions, while the FtSaBs behave more like cations that strongly associate with the solid phase relative to groundwater. Thus, the sorption mechanisms of the FtSs, FtSaBs, and 6:2 FtSaAm are more complex than expected and cannot be predicted by bulk soil properties.

Persistence and partitioning of eight selected pharmaceuticals in the aquatic environment: laboratory photolysis, biodegradation, and sorption experiments.

PubMed

Yamamoto, Hiroshi; Nakamura, Yudai; Moriguchi, Shigemi; Nakamura, Yuki; Honda, Yuta; Tamura, Ikumi; Hirata, Yoshiko; Hayashi, Akihide; Sekizawa, Jun

2009-02-01

We selected eight pharmaceuticals with relatively high potential ecological risk and high consumption-namely, acetaminophen, atenolol, carbamazepine, ibuprofen, ifenprodil, indomethacin, mefenamic acid, and propranolol-and conducted laboratory experiments to examine the persistence and partitioning of these compounds in the aquatic environment. In the results of batch sunlight photolysis experiments, three out of eight pharmaceuticals-propranolol, indomethacin, and ifenprodil-were relatively easily photodegraded (i.e., half-life<24h), whereas the other five pharmaceuticals were relatively stable against sunlight. The results of batch biodegradation experiments using river water suggested relatively slow biodegradation (i.e., half-life>24h) for all eight pharmaceuticals, but the rate constant was dependent on sampling site and time. Batch sorption experiments were also conducted to determine the sorption coefficients to river sediments and a model soil sample. The determined coefficients (K(d) values) were much higher for three amines (atenolol, ifenprodil, and propranolol) than for neutral compounds or carboxylic acids; the K(d) values of the amines were comparable to those of a four-ring polycyclic aromatic hydrocarbon (PAH) pyrene. The coefficients were also higher for sediment/soil with higher organic content, and the organic carbon-based sorption coefficient (logK(oc)) showed a poor linear correlation with the octanol-water distribution coefficient (logD(ow)) at neutral pH. These results suggest other sorption mechanisms-such as electrochemical affinity, in addition to hydrophobic interaction-play an important role in sorption to sediment/soil at neutral pH.

Sorption and solubility of ofloxacin and norfloxacin in water-methanol cosolvent.

PubMed

Peng, Hongbo; Li, Hao; Wang, Chi; Zhang, Di; Pan, Bo; Xing, Baoshan

2014-05-01

Prediction of the properties and behavior of antibiotics is important for their risk assessment and pollution control. Theoretical calculation was incorporated in our experimental study to investigate the sorption of ofloxacin (OFL) and norfloxacin (NOR) on carbon nanotubes and their solubilities in water, methanol, and their mixture. Sorption for OFL and NOR decreased as methanol volume fractions (fc) increased. But the log-linear cosolvency model could not be applied as a general model to describe the cosolvent effect on OFL and NOR sorption. We computed the bond lengths of possible hydrogen bonds between solute and solvent and the corresponding interaction energies using Density Functional Theory. The decreased OFL solubility with increased fc could be attributed to the generally stronger hydrogen bond between OFL and H2O than that between OFL and CH3OH. Solubility of NOR varied nonmonotonically with increasing fc, which may be understood from the stronger hydrogen bond of NOR-CH3OH than NOR-H2O at two important sites (-O18 and -O21). The interaction energies were also calculated for the solute surrounded by solvent molecules at all the possible hydrogen bond sites, but it did not match the solubility variations with fc for both chemicals. The difference between the simulated and real systems was discussed. Similar sorption but different solubility of NOR and OFL from water-methanol cosolvent suggested that sorbate-solvent interaction seems not control their sorption. Copyright © 2013 Elsevier Ltd. All rights reserved.

The effect of microbial activity and adsorption processes on groundwater dissolved organic carbon character and concentration

NASA Astrophysics Data System (ADS)

Meredith, K.; McDonough, L.; Oudone, P.; Rutlidge, H.; O'Carroll, D. M.; Andersen, M. S.; Baker, A.

2017-12-01

Balancing the terrestrial global carbon budget has proven to be a significant challenge. Whilst the movement of carbon in the atmosphere, rivers and oceans has been extensively studied, the potential for groundwater to act as a carbon source or sink through both microbial activity and sorption to and from mineral surfaces, is poorly understood. To investigate the biodegradable component of groundwater dissolved organic carbon (DOC), groundwater samples were collected from multiple coastal and inland sites. Water quality parameters such as pH, electrical conductivity, temperature, dissolved oxygen were measured in the field. Samples were analysed and characterised for their biodegradable DOC content using spectrofluorometric and Liquid Chromatography-Organic Carbon Detection (LC-OCD) techniques at set intervals within a 28 day period. Further to this, we performed laboratory sorption experiments on our groundwater samples using different minerals to examine the effect of adsorption processes on DOC character and concentration. Calcium carbonate, quartz and iron coated quartz were heated to 400ºC to remove potential carbon contamination, and then added at various known masses (0 mg to 10 g) to 50 mL of groundwater. Samples were then rotated for two hours, filtered at 0.2 μm and analysed by LC-OCD. This research forms part of an ongoing project which will assist in identifying the factors affecting the mobilisation, transport and removal of DOC in uncontaminated groundwater. By quantifying the relative importance of these processes, we can then determine whether the groundwater is a carbon source or sink. Importantly, this information will help guide policy and identify the need to include groundwater resources as part of the carbon economy.

Equilibrium and kinetic modeling of contaminant immobilization by activated carbon amended to sediments in the field.

PubMed

Rakowska, Magdalena I; Kupryianchyk, Darya; Koelmans, Albert A; Grotenhuis, Tim; Rijnaarts, Huub H M

2014-12-15

Addition of activated carbons (AC) to polluted sediments and soils is an attractive remediation technique aiming at reducing pore water concentrations of hydrophobic organic contaminants (HOCs). In this study, we present (pseudo-)equilibrium as well as kinetic parameters for sorption of a series of PAHs and PCBs to powdered and granular activated carbons (AC) after three different sediment treatments: sediment mixed with powdered AC (PAC), sediment mixed with granular AC (GAC), and addition of GAC followed by 2 d mixing and subsequent removal ('sediment stripping'). Remediation efficiency was assessed by quantifying fluxes of PAHs towards SPME passive samplers inserted in the sediment top layer, which showed that the efficiency decreased in the order of PAC > GAC stripping > GAC addition. Sorption was very strong to PAC, with Log KAC (L/kg) values up to 10.5. Log KAC values for GAC ranged from 6.3-7.1 and 4.8-6.2 for PAHs and PCBs, respectively. Log KAC values for GAC in the stripped sediment were 7.4-8.6 and 5.8-7.7 for PAH and PCB. Apparent first order adsorption rate constants for GAC (kGAC) in the stripping scenario were calculated with a first-order kinetic model and ranged from 1.6 × 10(-2) (PHE) to 1.7 × 10(-5) d(-1) (InP). Sorption affinity parameters did not change within 9 months post treatment, confirming the longer term effectiveness of AC in field applications for PAC and GAC. Copyright © 2014. Published by Elsevier Ltd.

Cadmium removal by bioclastic granules (Lithothamnium calcareum): batch and fixed-bed column systems sorption studies.

PubMed

Veneu, Diego Macedo; Schneider, Claudio Luiz; de Mello Monte, Marisa Bezerra; Cunha, Osvaldo Galvão Caldas; Yokoyama, Lídia

2018-07-01

The potential of Bioclastic Granules - BG (calcium-carbonate-based material) using the algae Lithothamnium calcareum as sorbent for the removal of Cd(II) from aqueous solutions by sorption was evaluated through batch and continuous systems tests using a fixed-bed column. Sorption process variables, in particular pH (2-7), particle size (<38-300 μm), initial BG concentration (0.1-1.0 g L -1 ), initial Cd(II) concentrations (5-400 mg L -1 ) and contact time (5-240 min), were evaluated. Adsorption isotherm profiles of Cd(II) per BG were similar to an L-type, or Langmuir type, with the adsorption forming a monolayer of approximately 0.61 μm, with a q max of 188.74 mg g -1 and k L of 0.710 L mg -1 . Thomas's model considers that sorption is not limited to a chemical reaction but is controlled by mass transfer at the interface. In the present study, the obtained value of k Th was 0.895 mL h -1  mg -1 , reaching a sorption capacity q o of 124.4 mg g -1 . For the Yoon-Nelson model, it was possible to obtain two important parameters to describe the behavior of the column, the rate constant (k YN ), obtaining a value of 0.09 h -1 and an τ of 82.12 h corresponding to the time required for sorption to occur of 50% of the solute in the rupture curve. X-ray diffraction and scanning electron microscopy analyses coupled to the X-ray dispersive energy system (SEM/EDS) of the BG after the Cd(II) ion sorption tests evidenced the formation of crystals with the prevalence of a new mineral phase (otavite).

Properties of biochar-amended soils and their sorption of imidacloprid, isoproturon, and atrazine.

PubMed

Jin, Jie; Kang, Mingjie; Sun, Ke; Pan, Zezhen; Wu, Fengchang; Xing, Baoshan

2016-04-15

Biochars produced from rice straw, wheat straw and swine manure at 300, 450 and 600°C were added to soil at 1, 5, 10, or 20% levels to determine whether they would predictably reduce the pore water concentration of imidacloprid, isoproturon, and atrazine. The sorption capacity of the mixtures increased with increasing biochar amounts. The enhanced sorption capacity could be attributed to the increased organic carbon (OC) content and surface area (SA) as well as the decreased hydrophobicity. Biochar dominated the overall sorption when its content was above 5%. The OC contents of the mixtures with 10% and 20% biochar were generally lower than the predicted values. This implies possible interaction between soil components and biochar and/or the effect of biochar oxidation. For soils amended with biochars produced at 300°C, the N2 SA (N2-SA) values were underestimated. The predicted CO2 SA (CO2-SA) values of the mixtures at the biochar content of 10% and 20% were generally higher than the experimental values. Sorption of imidacloprid to the soils amended with biochar at 10% and 20% levels, excluding the soils amended with rice (SR300) and wheat (SW300) straw-derived biochar produced at 300°C, was lower than the predicted value. For SR300 and SW300, the intrinsic sorption capacity of biochar was enhanced by 1.3-5.6 times, depending on the biochar, solute concentration, and biochar dose. This study indicates that biochars would be helpful to stabilize the soil contaminated with imidacloprid, isoproturon, and atrazine, but the sorption capacity of the mixtures could exceed or fall short of predicted values without assuming a cross-effect between soil and biochar. Copyright © 2016 Elsevier B.V. All rights reserved.

Equilibrium sorption and diffusion rate studies with halogenated organic chemical and sandy aquifer material

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ball, W.P.

1990-01-01

Concepts for rate limitation of sorptive uptake of hydrophobic organic solutes by aquifer solids are reviewed, emphasizing physical diffusion models and in the context of effects on contaminant transport. Data for the sorption of tetrachloroethene (PCE) and 1,2,4,5-tetrachlorobenzene (TeCB) on Borden sand are presented, showing that equilibrium is attained very slowly, requiring equilibration times on the order of tens of days for PCE and hundreds of days for TeCB. The rate of approach to equilibrium decreased with increasing particle size and sorption distribution coefficient, in accordance with retarded intragranular diffusion models. Pulverization of the samples significantly decreased the required timemore » to equilibrium without changing the sorption capacity of the solids. Batch sorption methodology was refined to allow accurate measurement of long-term distribution coefficients, using purified {sup 14}C-labelled solute spikes and sealed glass ampules. Sorption isotherms for PCE and TeCB were conducted with size fractions of Borden sand over four to five orders of magnitude in aqueous concentration, and were found to be slightly nonlinear (Freundlich exponent = 0.8). A concentrated set of data in the low concentration range (<50 ug/L) revealed that sorption in this range could be equally well described by a linear isotherm. Distribution coefficients of the two solutes with seven size fractions of Borden sand, measured at low concentration and at full equilibrium, were between seven and sixty times the value predicted on the basis of recent correlations with organic carbon content. Rate results for coarse size fractions support a simple pore diffusion model, with pore diffusion coefficients estimated to be approximately 3 {times} 10{sup {minus}8} cm{sup 2}/sec, more than 200{times} lower than the aqueous diffusivities.« less

Describing sorption of pharmaceuticals to lake and river sediments, and sewage sludge from UNESCO Biosphere Reserve Kristianstads Vattenrike by chromatographic asymmetry factors and recovery measurements.

PubMed

Svahn, Ola; Björklund, Erland

2015-10-09

Over the past 30 years a vast number of studies have demonstrated the presence of pharmaceutical residues in the environment. But still knowledge is scarce regarding the interaction of these emerging pollutants with various matrices in nature. A chromatographic system with on-line detection was developed to perform a sorption study of six selected pharmaceuticals to four natural sediments and dewatered digested sewage treatment plant sludge with differing physicochemical characteristics. Sorption effects, measured as asymmetry factors and recoveries, differed pronouncedly among the pharmaceuticals and between the matrices, which could be explained by basic physicochemical properties of the investigated compounds in relation to matrix characteristics. Protonated and deprotonated molecular properties had the greatest importance for sorbate-sorbent interactions. Atenolol, with cationic properties, showed the highest degree of sorption regardless of the matrix studied. Diclofenac and furosemide, both acids, showed the least tendency towards interactions to natural matrices. Among the neutral compounds bendroflumethiazide, carbamazepine and oxazepam, weaker forces, such as van der Waals, aromatic electron donor-acceptor interactions, and hydrogen forces, seemed more important to determine sorption differences. Results revealed that sorption of pharmaceuticals on natural sediments decreased in the order: atenolol (+)>bendroflumethiazide>oxazepam>carbamazepine>diclofenac (-)>furosemide (-). The matrix content of organic matter measured as total organic carbon (TOC) clearly dictated drug sorption. Beside from studying matrix interaction, these results and the developed technique and methodology might find use in the development of new removal processes of pharmaceuticals from wastewater based on improved knowledge concerning chemical interactions to filter materials. Copyright © 2015 Elsevier B.V. All rights reserved.

COSOLVENT EFFECTS ON ORGANIC CHEMICAL PARTITIONING TO SEDIMENT ORGANIC CARBON

EPA Science Inventory

Sorption-desorption hysteresis, slow desorption kinetics and resultant bioavailability, and other nonideal phenomena have been attributed to the differing sorptive characteristics of the natural organic polymers associated with soils and sediments. The objectives of this study we...

PROCESS OF RECOVERING ALKALI METALS

DOEpatents

Wolkoff, J.

1961-08-15

A process is described of recovering alkali metal vapor by sorption on activated alumina, activated carbon, dehydrated zeolite, activated magnesia, or Fuller's earth preheated above the vaporization temperature of the alkali metal and subsequent desorption by heating the solvent under vacuum. (AEC)

Removal of dissolved textile dyes from wastewater by a compost sorbent

USGS Publications Warehouse

Tsui, L.S.; Roy, W.R.; Cole, M.A.

2003-01-01

The objective of this study was to evaluate the potential for treating dye-contaminated waste streams by sorption using compost as a low-cost sorbent. A mature, thermophilic compost sample was used to sorb CI Acid Black 24, CI Acid Orange 74, CI Basic Blue 9, CI Basic Green 4, CI Direct Blue 71, CI Direct Orange 39, CI Reactive Orange 16 and CI Reactive Red 2 from solution using a batch-sorption method. With the exception of the two reactive dyes, the sorption kinetics were favourable for a continuous-flow treatment process with the compost-dye mixtures reaching a steady state within 3-5 h. Based on limited comparisons, the affinity of the compost for each dye appeared to be competitive with other non-activated carbon sorbents. The results suggest that additional research on using compost as a sorbent for dye-contaminated solutions is warranted.

The removal of uranium (VI) from aqueous solutions onto activated carbon developed from grinded used tire.

PubMed

Belgacem, Ahmed; Rebiai, Rachid; Hadoun, Hocine; Khemaissia, Sihem; Belmedani, Mohamed

2014-01-01

In this study, activated carbon was prepared from waste tire by KOH chemical activation. The pore properties including the BET surface area, pore volume, pore size distribution, and average pore diameter were characterized. BET surface area of the activated carbon was determined as 558 m(2)/g. The adsorption of uranium ions from the aqueous solution using this activated carbon has been investigated. Various physico-chemical parameters such as pH, initial metal ion concentration, and adsorbent dosage level and equilibrium contact time were studied by a batch method. The optimum pH for adsorption was found to be 3. The removal efficiency has also been determined for the adsorption system as a function of initial concentration. The experimental results were fitted to Langmuir, Freundlich, and Dubinin-Radushkevich (D-R) isotherm models. A comparison of best-fitting was performed using the coefficient of correlation and the Langmuir isotherm was found to well represent the measured sorption data. According to the evaluation using the Langmuir equation, the saturated monolayer sorption capacity of uranium ions onto waste tire activated carbon was 158.73 mg/g. The thermodynamic equilibrium constant and the Gibbs free energy were determined and results indicated the spontaneous nature of the adsorption process. Kinetics data were best described by pseudo-second-order model.

In situ modification of activated carbons developed from a native invasive wood on removal of trace toxic metals from wastewater.

PubMed

de Celis, J; Amadeo, N E; Cukierman, A L

2009-01-15

Activated carbons were developed by phosphoric acid activation of sawdust from Prosopis ruscifolia wood, an indigenous invasive species of degraded lands, at moderate conditions (acid/precursor ratio=2, 450 degrees C, 0.5h). For in situ modification of their characteristics, either a self-generated atmosphere or flowing air was used. The activated carbons developed in the self-generated atmosphere showed higher BET surface area (2281m2/g) and total pore volume (1.7cm3/g) than those obtained under flowing air (1638m2/g and 1.3cm3/g). Conversely, the latter possessed a higher total amount of surface acidic/polar oxygen groups (2.2meq/g) than the former (1.5meq/g). To evaluate their metal sorption capability, adsorption isotherms of Cu(II) ion from model solutions were determined and properly described by the Langmuir model. Maximum sorption capacity (Xm) for the air-derived carbons (Xm=0.44mmol/g) almost duplicated the value for those obtained in the self-generated atmosphere (Xm=0.24mmol/g), pointing to a predominant effect of the surface functionalities on metal sequestering behaviour. The air-derived carbons also demonstrated a superior effectiveness in removing Cd(II) ions as determined from additional assays in equilibrium conditions. Accordingly, effective phosphoric acid-activated carbons from Prosopis wood for toxic metals removal from wastewater may be developed by in situ modification of their characteristics operating under flowing air.

Black carbon inclusive multichemical modeling of PBDE and PCB biomagnification and -transformation in estuarine food webs.

PubMed

Di Paolo, Carolina; Gandhi, Nilima; Bhavsar, Satyendra P; Van den Heuvel-Greve, Martine; Koelmans, Albert A

2010-10-01

Bioavailability and bioaccumulation of polybrominated diphenylethers (PBDEs) are affected by adsorption on black carbon (BC) and metabolism in biota, respectively. Recent studies have addressed these two processes separately, illustrating their importance in assessing contaminant dynamics. In order to properly examine biomagnification of polychlorinated biphenyls (PCBs) and PBDEs in an estuarine food-web, here we set up a black carbon inclusive multichemical model. A dual domain sorption model, which accounted for sorption to organic matter (OM) and black carbon (BC), was used to estimate aqueous phase concentrations from the measured chemical concentrations in suspended solids. We adapted a previously published multichemical model that tracks the movement of a parent compound and its metabolites in each organism and within its food web. First, the model was calibrated for seven PCB congeners assuming negligible metabolism. Subsequently, PBDE biomagnification was modeled, including biotransformation and bioformation of PBDE congeners, keeping the other model parameters the same. The integrated model was capable of predicting trophic magnification factors (TMF) within error limits. PBDE metabolic half-lives ranged 21-415 days and agreed to literature data. The results showed importance of including BC as an adsorbing phase, and biotransformation and bioformation of PBDEs for a proper assessment of their dynamics in aquatic systems.

Surface carbon influences on the reductive transformation of TCE in the presence of granular iron.

PubMed

Firdous, R; Devlin, J F

2018-04-05

To gain insight into the processes of transformations in zero-valent iron systems, electrolytic iron (EI) has been used as a surrogate for the commercial products actually used in barriers. This substitution facilitates mechanistic studies, but may not be fully representative of all the relevant processes at work in groundwater remediation. To address this concern, the kinetic iron model (KIM) was used to investigate sorption and reactivity differences between EI and Connelly brand GI, using TCE as a probe compound. It was observed that retardation factors (R app ) for GI varied non-linearly with influent concentrations to the columns (C o ), and declined significantly as GI aged. In contrast, R app values for EI were small and insensitive to C o , and changed minimally with iron aging. Moreover, although declines in the rate constants (k) and increases in the sorption coefficients were observed for both iron types, they were most pronounced in the case of EI. SEM scans of the EI surface before and after aging (90 days) established the appearance of carbon on the older surface. This work provides evidence that iron with a higher surface carbon content outperforms pure iron, suggesting that the carbon is actively involved in promoting TCE reduction. Copyright © 2017 Elsevier B.V. All rights reserved.

Interactions of low molecular weight aromatic acids and amino acids with goethite, kaolinite and bentonite with or without organic matter coating

NASA Astrophysics Data System (ADS)

Gao, Jiajia; Jansen, Boris; Cerli, Chiara; Kalbitz, Karsten

2015-04-01

Interaction of organic matter molecules with the soil's solid phase is a key factor influencing the stabilization of carbon in soils and thus forms a crucial aspect of the global carbon cycle. While subject of much research attention so far, we still have much to learn about such interactions at the molecular level; in particular in the light of competition between different classes of organic molecules and in the presence of previously adsorbed soil organic matter. We studied the interaction of a group of low molecular weight (LMW) aromatic acids (salicylic, syringic, vanillic and ferulic acid) and amino acids (lysine, glutamic, leucine and phenylalanine) on goethite, kaolinite and bentonite with and without previously adsorbed dissolved organic matter (DOM). For this we used batch experiments at pH = 6.0 where some of the organic compounds were positively charged (i.e. lysine) or negatively charged (i.e. glutamic and salicylic acid) while the minerals also displayed positively (i.e. goethite) or negatively charged surfaces (i.e. bentonite). We found much higher sorption of salicylic acid and lysine than other compounds. On the bare minerals we found a great variety of sorption strength, with salicylic acid strongly adsorbed, while syringic, vanillic and ferulic acid showed little or no adsorption. For the amino acids, protonated lysine showed a stronger affinity to negatively charged kaolinite and bentonite than other amino acids. While deprotonated glutamic acid showed the strongest adsorption on goethite. Leucine and phenylalanine showed hardly any adsorption on any of the minerals. When present concurrently, amino acids decreased the sorption of salicylic acid on the three types of mineral, while the presence of LMW aromatic acids increased the sorption of lysine on kaolinite and bentonite and the sorption of glutamic acid on goethite. The presence of previously adsorbed DOM reduced the sorption of salicylic acid and lysine. The results confirm that interactions of different classes of organic molecules with solid soil phases cannot be understood in isolation, but must be interpreted in the context of the presence of other classes of molecules. It seems that the presence of methoxy groups decreases the adsorption of aromatic acids to minerals. We did not find evidence for protein conditioning of any mineral surface, i.e. increased adsorption of aromatic acids after adsorption of amino acids.

Sorption of Cm(III) and Eu(III) onto clay minerals under saline conditions: Batch adsorption, laser-fluorescence spectroscopy and modeling

NASA Astrophysics Data System (ADS)

Schnurr, Andreas; Marsac, Rémi; Rabung, Thomas; Lützenkirchen, Johannes; Geckeis, Horst

2015-02-01

The present work reports experimental data for trivalent metal cation (Cm/Eu) sorption onto illite (Illite du Puy) and montmorillonite (Na-SWy-2) in NaCl solutions up to 4.37 molal (m) in the absence of carbonate. Batch sorption experiments were carried out for a given ionic strength at fixed metal concentration (mEu = 2 × 10-7 m, labeled with 152Eu for γ-counting) and at a constant solid to liquid ratio (S:L = 2 g/L) for 3 < pHm < 12 (pHm = -log mH+). The amount of clay sorbed Eu approaches almost 100% (with log KD > 5) for pHm > 8, irrespective of the NaCl concentration. Variations in Eu uptake are minor at elevated NaCl concentrations. Time-resolved laser fluorescence spectroscopy (TRLFS) studies on Cm sorption covering a wide range of NaCl concentrations reveal nearly identical fluorescence emission spectra after peak deconvolution, i.e. no significant variation of Cm surface speciation with salinity. Beyond the three surface complexes already found in previous studies an additional inner-sphere surface species with a fluorescence peak maximum at higher wavelength (λ ∼ 610 nm) could be resolved. This new surface species appears in the high pH range and is assumed to correspond to a clay/curium/silicate complex as already postulated in the literature for kaolinite. The 2 site protolysis non-electrostatic surface complexation and cation exchange sorption model (2SPNE SC/CE) was applied to describe Eu sorption data by involving the Pitzer and SIT (specific ion interaction) formalism in the calculation of the activities of dissolved aqueous species. Good agreement of model and experiment is achieved for sorption data at pHm < 6 without the need of adjusting surface complexation constants. For pHm > 6 in case of illite and pHm > 8 in case of montmorillonite calculated sorption data systematically fall below experimental data with increasing ionic strength. Under those conditions sorption is almost quantitative and deviations must be discussed considering uncertainties of measured Eu concentrations in the range of analytical detection limits.

Attenuation of phenanthrene and pyrene adsorption by sewage sludge-derived biochar in biochar-amended soils.

PubMed

Zielińska, Anna; Oleszczuk, Patryk

2016-11-01

The aim of this study was to evaluate the effect of soils on the sorption of phenanthrene (PHE) and pyrene (PYR) by sewage sludge-derived biochars (SS-derived biochars). The SS-derived biochars were added to soils with varying properties as well as with a different degree and source of polycyclic aromatic hydrocarbons (PAHs) contamination. The biochars (BCs) were produced from sewage sludge during pyrolysis at temperatures of 500 °C (BC500) and 700 °C (BC700). The addition of biochars to the soils (5 %, w/w) increased the sorption of PHE from 8.3 to 20.3 % and PYR from 14.5 to 31.7 % by amended soil. BC700 biochar was characterized by better sorption capacity than BC500 biochar. Nevertheless, the presence of soil reduces the effectiveness of biochars in binding the compounds studied. The sorption capacity of the biochars decreased several times after they had been mixed with the soil compared to pure biochars. The study found dissolved organic carbon (DOC) and clay minerals present in the soils to have a significant effect on reducing the efficiency of PHE and PYR sorption by biochar. A greater impact of fouling was observed in the case of BC500 biochar characterized by lower porosity than BC700 biochar.

Wicking of light hydrophobic liquid phase from water by pulverized rubber: Theoretical and experimental analyses.

PubMed

Boglaienko, Daria; Tansel, Berrin

2017-03-05

Pulverized rubber (PR) can be utilized for capturing floating oils to prevent spreading and volatilization of hydrocarbons. Experiments were conducted using PR with four different particle sizes (ranging from 0.075 to 0.600mm) and South Louisiana crude oil. The oil capture performance of the PR particles was compared with that of powdered activated carbon (AC). Oil-particle interactions were analyzed using capillary theories for lateral aggregation and wicking processes, as well as sorption capacity in relation to particle size. The sorption capacity (as oil to sorbent ratio) for PR with particle size 0.115mm (4.41g/g) was comparable to that of AC with particle size 0.187mm (5.00g/g). Sorption efficiency (oil:powder ratio, g/g) of the PR increased with decreasing particle size. Sorption of oil by PR occurred rapidly (in less than 10min) which indicated strong capillary action. No additional sorption occurred after 30min. For the PR sample with larger particle size (0.600-0.400mm), lateral aggregation was clearly noticeable. The PR-oil aggregates could be easily removed from the water surface without breaking. The cost, availability and recycling potential of PR make it a feasible alternative material for oil spill response and industrial applications which require removal of floating oils. Copyright © 2016 Elsevier B.V. All rights reserved.

Adsorption of copper (II) by using derived-farmyard and poultry manure biochars: Efficiency and mechanism

NASA Astrophysics Data System (ADS)

Batool, Saima; Idrees, Muhammad; Hussain, Qaiser; Kong, Jie

2017-12-01

Biochar (BC) has recently become an attractive adsorbent for the removal of toxic metals from aqueous media. In this study, the adsorption efficiency of BCs derived through farmyard and poultry manure (DBC-FYM, DBC-PM) for the removal of copper (Cu2+) from water was evaluated. The porosity, surface structure, internal morphology, thermal stability and functional groups of the DBCs were analyzed using different analytical techniques such as scanning electron microscopy (SEM), X-ray photon spectroscopy (XPS), thermogravimetric analyses (TGA) and fourier transmission infrared spectroscopy (FTIR). Kinetics and isothermal data were acquired by batch adsorption mode. The isothermal sorption data was well correlated (R2 > 0.98) with the Freundlich model describing multilayer sorption of Cu2+ on heterogeneous DBCs surface. The maximum Cu2+ sorption was estimated as 44.50 mg/g for DBC-FYM and 43.68 mg/g for DBC-PM. The sorption data followed the pseudo-second order kinetics, indicating the chemical interaction between Cu2+ and the negative charged surface of DBCs. The thermodynamic parameters indicated that the reaction was exothermic and spontaneous. Post-sorption analysis of the DBCs by XPS suggested the formation of CuO and carbonate dihydroxide. The outcomes of the present study indicated that DBCs could be valuable green sorbents for removing Cu2+ from contaminated aqueous media.

Sorption of selected pharmaceuticals and pesticides on different river sediments.

PubMed

Radović, Tanja T; Grujić, Svetlana D; Kovačević, Srđan R; Laušević, Mila D; Dimkić, Milan A

2016-12-01

In the present work, the sorption ability of 17 pharmaceutical compounds, two metabolites, and 15 pesticides (34 target compounds in total) onto four different river sediments was investigated separately. Selected compounds present the most frequently prescribed pharmaceuticals in human and animal medicine and the most frequently used pesticides in agriculture. Their presence into the surface, ground, and waste waters was confirmed into the numerous papers in literature, as well as their presence into the river sediments (for some of them). However, investigations of their sorption onto the river sediments, as major natural protection from potential pollution of ground water by them is missing. Sorption in this study was investigated onto river sediments taken from rivers in the Republic of Serbia, where only less than 10 % of total generated waste water passes through mainly basic treatment processes. Experiments were based on batch equilibrium procedures and obtained solutions were analyzed by previously developed and validated sensitive high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) analytical methods. All results were modeled by Freundlich isotherms. Obtained results have shown that Kf coefficient values are in correlation with organic carbon content. Kd sorption coefficient values were relatively low and ranged in wide ranges for almost all compounds and sediments. That implicates on the conclusion that capacities of the investigated sorbents are not large for those compounds.

Kinetics and isotherm analysis of 2,4-dichlorophenoxyl acetic acid adsorption onto soil components under oxic and anoxic conditions.

PubMed

Ololade, Isaac A; Alomaja, Folasade; Oladoja, Nurudeen A; Ololade, Oluwaranti O; Oloye, Femi F

2015-01-01

2,4-dichlorophenoxyl acetic acid (2,4-D, pKa = 2.8) is used extensively as a herbicide in agricultural practices. Its sorption behavior on both untreated and soils treated to significantly remove specific components (organic and iron and manganese [Fe-Mn] oxides and hydroxides phases) was investigated under oxic and anoxic conditions. The chemical and structural heterogeneity of the soil components were characterized by elemental analysis and X-ray diffraction (XRD). The coexistence of the various components seems to either mask sorption sites on the untreated soil surfaces or inhibit interlayer diffusion of 2,4-D. All sorption data conform to the Freundlich description and a pseudo-second-order kinetic model. There was a strong positive correlation between sorption capacity K(d), and surface area (r(2) ≤ 0.704), but a negative correlation was uncovered with both pH and organic carbon (r(2) ≤ -0.860). The results indicate that 2,4-D is preferably sorbed under oxic rather than anoxic conditions and it is greater on soils containing a high Fe content. There was incomplete 2,4-D sorption reversibility, with desorption occurring more rapidly under anoxic conditions. The study suggests that stimulation of Fe III reduction could be used for the bioremediation of a 2,4-D-contaminated site.

Sorption of selected pesticides on soils, sediment and straw from a constructed agricultural drainage ditch or pond.

PubMed

Vallée, Romain; Dousset, Sylvie; Billet, David; Benoit, Marc

2014-04-01

Buffer zones such as ponds and ditches are used to reduce field-scale losses of pesticides from subsurface drainage waters to surface waters. The objective of this study was to assess the efficiency of these buffer zones, in particular constructed wetlands, focusing specifically on sorption processes. We modelled the sorption processes of three herbicides [2-methyl-4-chlorophenoxyacetic acid (2,4-MCPA), isoproturon and napropamide] and three fungicides (boscalid, prochloraz and tebuconazole) on four substrates (two soils, sediment and straw) commonly found in a pond and ditch in Lorraine (France). A wide range of Freundlich coefficient (K fads) values was obtained, from 0.74 to 442.63 mg(1 - n) L (n) kg(-1), and the corresponding K foc values ranged from 56 to 3,725 mg(1 - n) L (n) kg(-1). Based on potential retention, the substrates may be classified as straw > sediments > soils. These results show the importance of organic carbon content and nature in the process of sorption. Similarly, the studied pesticides could be classified according to their adsorption capacity as follows: prochloraz > tebuconazole-boscalid > napropamide > MCPA-isoproturon. This classification is strongly influenced by the physico-chemical properties of pesticides, especially solubility and K oc. Straw exhibited the largest quantity of non-desorbable pesticide residues, from 12.1 to 224.2 mg/L for all pesticides. The presence of plants could increase soil-sediment sorption capacity. Thus, establishment and maintenance of plants and straw filters should be promoted to optimise sorption processes and the efficiency of ponds and ditches in reducing surface water pollution.

The effect of grain size and surface area on organic matter, lignin and carbohydrate concentration, and molecular compositions in Peru Margin sediments

USGS Publications Warehouse

Bergamaschi, B.A.; Tsamakis, E.; Keil, R.G.; Eglinton, T.I.; Montlucon, D.B.; Hedges, J.I.

1997-01-01

A C-rich sediment sample from the Peru Margin was sorted into nine hydrodynamically-determined grain size fractions to explore the effect of grain size distribution and sediment surface area on organic matter content and composition. The neutral monomeric carbohydrate composition, lignin oxidation product yields, total organic carbon, and total nitrogen contents were determined independently for each size fraction, in addition to sediment surface area and abundance of biogenic opal. The percent organic carbon and percent total nitrogen were strongly related to surface area in these sediments. In turn, the distribution of surface area closely followed mass distribution among the textural size classes, suggesting hydrodynamic controls on grain size also control organic carbon content. Nevertheless, organic compositional distinctions were observed between textural size classes. Total neutral carbohydrate yields in the Peru Margin sediments were found to closely parallel trends in total organic carbon, increasing in abundance among grain size fractions in proportion to sediment surface area. Coincident with the increases in absolute abundance, rhamnose and mannose increased as a fraction of the total carbohydrate yield in concert with surface area, indicating these monomers were preferentially represented in carbohydrates associated with surfaces. Lignin oxidation product yields varied with surface area when normalized to organic carbon, suggesting that the terrestrially-derived component may be diluted by sorption of marine derived material. Lignin-based parameters suggest a separate source for terrestrially derived material associated with sand-size material as opposed to that associated with silts and clays. Copyright ?? 1997 Elsevier Science Ltd.

The effect of grain size and surface area on organic matter, lignin and carbohydrate concentration, and molecular compositions in Peru Margin sediments

NASA Astrophysics Data System (ADS)

Bergamaschi, Brian A.; Tsamakis, Elizabeth; Keil, Richard G.; Eglinton, Timothy I.; Montluçon, Daniel B.; Hedges, John I.

1997-03-01

A C-rich sediment sample from the Peru Margin was sorted into nine hydrodynamically-determined grain size fractions to explore the effect of grain size distribution and sediment surface area on organic matter content and composition. The neutral monomeric carbohydrate composition, lignin oxidation product yields, total organic carbon, and total nitrogen contents were determined independently for each size fraction, in addition to sediment surface area and abundance of biogenic opal. The percent organic carbon and percent total nitrogen were strongly related to surface area in these sediments. In turn, the distribution of surface area closely followed mass distribution among the textural size classes, suggesting hydrodynamic controls on grain size also control organic carbon content. Nevertheless, organic compositional distinctions were observed between textural size classes. Total neutral carbohydrate yields in the Peru Margin sediments were found to closely parallel trends in total organic carbon, increasing in abundance among grain size fractions in proportion to sediment surface area. Coincident with the increases in absolute abundance, rhamnose and mannose increased as a fraction of the total carbohydrate yield in concert with surface area, indicating these monomers were preferentially represented in carbohydrates associated with surfaces. Lignin oxidation product yields varied with surface area when normalized to organic carbon, suggesting that the terrestrially-derived component may be diluted by sorption of marine derived material. Lignin-based parameters suggest a separate source for terrestrially derived material associated with sand-size material as opposed to that associated with silts and clays.

Do Vertical Gradients in Soil Environmental Conditions Regulate Exudation Rates from Peatland Vegetation?

NASA Astrophysics Data System (ADS)

Proctor, C.; He, Y.

2017-12-01

Deposition of carbon belowground via the root exudation pathway is the net of root-borne efflux and influx processes. For select exudates, root have a remarkable ability to actively recapture lost compounds, suggesting that influx mechanisms regulate exudation. However, roots are not the sole sink for root effluxed carbon. Roots compete with solute sorption and microbial uptake, whom are regulated by a unique set of soil environmental conditions. Peatland soil features stark vertical gradients in their physical, chemical, biological, and hydrological properties, which has downstream implications for the relative competitive ability of each actor in root-soil-microbial interactions. This study developed a single root exudate model using the Barber-Cushman approach to examine the radial accumulation of exudates in simulated peatland soil with vertical gradients. The model simulated efflux, influx, solute diffusion, solute mineralization and solid phase sorption mechanisms as depth dependent on bulk density, porosity, tortuosity, buffer power, temperature, and microbial biomass. Deeper peat soil reduced the porosity that permits solute transport, increased tortuosity which lowered the effective diffusion rate, increased solute-solid sorption, and reduced microbial mineralization of effluxed compounds. Slower mineralization rates were partially juxtaposed by increases in sorption, albeit the net removal of effluxed compounds was lower, leading to a larger amount of exudates to remain in the rhizosphere around deeper roots. Increase in the solid phase, and its subsequent constriction of solute migration, lead to a higher accumulation of effluxed compounds on the rhizoplane, up to 1.23x higher than shallow soil. Subsequently, influx mechanisms captured a larger fraction of effluxed compounds (69.06% at -10cm versus 84.8% at -80 cm), reducing net exudation rates from 0.641 to 0.315 nmol cm-1 hr-1 between -10 and -80cm depths. These results suggest that localized environmental conditions around roots can be a considerable influence on root influx and competition for root exudates. The insights provided by this model help provide a better understanding of exudate regulation in peatlands and the quantity and quality of carbon deposited to the methanogen community.

Drivers of dissolved organic carbon export in a subarctic catchment: Importance of microbial decomposition, sorption-desorption, peatland and lateral flow.

PubMed

Tang, Jing; Yurova, Alla Y; Schurgers, Guy; Miller, Paul A; Olin, Stefan; Smith, Benjamin; Siewert, Matthias B; Olefeldt, David; Pilesjö, Petter; Poska, Anneli

2018-05-01

Tundra soils account for 50% of global stocks of soil organic carbon (SOC), and it is expected that the amplified climate warming in high latitude could cause loss of this SOC through decomposition. Decomposed SOC could become hydrologically accessible, which increase downstream dissolved organic carbon (DOC) export and subsequent carbon release to the atmosphere, constituting a positive feedback to climate warming. However, DOC export is often neglected in ecosystem models. In this paper, we incorporate processes related to DOC production, mineralization, diffusion, sorption-desorption, and leaching into a customized arctic version of the dynamic ecosystem model LPJ-GUESS in order to mechanistically model catchment DOC export, and to link this flux to other ecosystem processes. The extended LPJ-GUESS is compared to observed DOC export at Stordalen catchment in northern Sweden. Vegetation communities include flood-tolerant graminoids (Eriophorum) and Sphagnum moss, birch forest and dwarf shrub communities. The processes, sorption-desorption and microbial decomposition (DOC production and mineralization) are found to contribute most to the variance in DOC export based on a detailed variance-based Sobol sensitivity analysis (SA) at grid cell-level. Catchment-level SA shows that the highest mean DOC exports come from the Eriophorum peatland (fen). A comparison with observations shows that the model captures the seasonality of DOC fluxes. Two catchment simulations, one without water lateral routing and one without peatland processes, were compared with the catchment simulations with all processes. The comparison showed that the current implementation of catchment lateral flow and peatland processes in LPJ-GUESS are essential to capture catchment-level DOC dynamics and indicate the model is at an appropriate level of complexity to represent the main mechanism of DOC dynamics in soils. The extended model provides a new tool to investigate potential interactions among climate change, vegetation dynamics, soil hydrology and DOC dynamics at both stand-alone to catchment scales. Copyright © 2017 Elsevier B.V. All rights reserved.

Metal Removal Efficiency And Ecotoxicological Assessment Of Field-Scale Passive Treatment Biochemical Reactors

EPA Science Inventory

Anaerobic biochemical reactors (BCRs) are useful for removing metals from mining-impacted water at remote sites. Removal processes include sorption and precipitation of metal sulfides, carbonates, and hydroxides. A question of interest is whether BCRs remove aquatic toxicity. ...

Ultrafast Carbon Dioxide Sorption Kinetics Using Lithium Silicate Nanowires.

PubMed

Nambo, Apolo; He, Juan; Nguyen, Tu Quang; Atla, Veerendra; Druffel, Thad; Sunkara, Mahendra

2017-06-14

In this paper, the Li 4 SiO 4 nanowires (NWs) were shown to be promising for CO 2 capture with ultrafast kinetics. Specifically, the nanowire powders exhibited an uptake of 0.35 g g -1 of CO 2 at an ultrafast adsorption rate of 0.22 g g -1 min -1 at 650-700 °C. Lithium silicate (Li 4 SiO 4 ) nanowires and nanopowders were synthesized using a "solvo-plasma" technique involving plasma oxidation of silicon precursors mixed with lithium hydroxide. The kinetic parameter values (k) extracted from sorption kinetics obtained using NW powders are 1 order of magnitude higher than those previously reported for the Li 4 SiO 4 -CO 2 reaction system. The time scales for CO 2 sorption using nanowires are approximately 3 min and two orders magnitude faster compared to those obtained using lithium silicate powders with spherical morphologies and aggregates. Furthermore, Li 4 SiO 4 nanowire powders showed reversibility through sorption-desorption cycles indicating their suitability for CO 2 capture applications. All of the morphologies of Li 4 SiO 4 powders exhibited a double exponential behavior in the adsorption kinetics indicating two distinct time constants for kinetic and the mass transfer limited regimes.

Hydrogen recombiner catalyst test supporting data

DOE Office of Scientific and Technical Information (OSTI.GOV)

Britton, M.D.

1995-01-19

This is a data package supporting the Hydrogen Recombiner Catalyst Performance and Carbon Monoxide Sorption Capacity Test Report, WHC-SD-WM-TRP-211, Rev 0. This report contains 10 appendices which consist of the following: Mass spectrometer analysis reports: HRC samples 93-001 through 93-157; Gas spectrometry analysis reports: HRC samples 93-141 through 93-658; Mass spectrometer procedure PNL-MA-299 ALO-284; Alternate analytical method for ammonia and water vapor; Sample log sheets; Job Safety analysis; Certificate of mixture analysis for feed gases; Flow controller calibration check; Westinghouse Standards Laboratory report on Bois flow calibrator; and Sorption capacity test data, tables, and graphs.

Sorption of mercury in soils with different humus content

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lodenius, M.; Seppaenen, A.; Autio S.

The strong sorption of mercury to humic matter in soil and water has raised the question about the influence of organic matter of different soil types on the mobilization of mercury from soil. Mercury is normally bound to humic and fulvic acids, which may be released in connection with flooding, draining and ditching. High mercury contents in fish from man-made lakes have been reported mainly from temperated regions. This has been assumed to be a result of the slower metabolism of methyl mercury in cool water but the effect of temperature on the mobilization process is still poorly known. Themore » sorption and leaching of mercury in three different soils was studied in vitro using a mercury concentrations near the natural level. Soil lysimeters were watered with distilled water or artificial acid rain at two temperatures.« less

Role of biotransformation, sorption and mineralization of (14)C-labelled sulfamethoxazole under different redox conditions.

PubMed

Alvarino, T; Nastold, P; Suarez, S; Omil, F; Corvini, P F X; Bouju, H

2016-01-15

(14)C-sulfamethoxazole biotransformation, sorption and mineralization was studied with heterotrophic and autotrophic biomass under aerobic and anoxic conditions, as well as with anaerobic biomass. The (14)C-radiolabelled residues distribution in the solid, liquid and gas phases was closely monitored along a total incubation time of 190 h. Biotransformation was the main removal mechanism, mineralization and sorption remaining below 5% in all the cases, although the presence of a carbon source exerted a positive effect on the mineralization rate by the aerobic heterotrophic bacteria. In fact, an influence of the type of primary substrate and the redox potential was observed in all cases on the biotransformation and mineralization rates, since an enhancement of the removal rate was observed when an external carbon source was used as a primary substrate under aerobic conditions, while a negligible effect was observed under nitrifying conditions. In the liquid phases collected from all assays, up to three additional peaks corresponding to (14)C-radiolabelled residues were detected. The highest concentration was observed under anaerobic conditions, where two radioactive metabolites were detected representing each around 15% of the total applied radioactivity after 180 h incubation. One of the metabolites detected under anoxic and anaerobic conditions, is probably resulting from ring cleavage of the isoxazole ring. Copyright © 2015 Elsevier B.V. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Edwin S. Olson; Kurt E. Eylands; Daniel J. Stepan

New federal drinking water regulations have been promulgated to restrict the levels of disinfection by-products (DBPs) in finished public water supplies. DBPs are suspected carcinogens and are formed when organic material is partially oxidized by disinfectants commonly used in the water treatment industry. Additional federal mandates are expected in the near future that will also affect public water suppliers with respect to DBPs. These new federal drinking water regulations may require public water suppliers to adjust treatment practices or incorporate additional treatment operations into their existing treatment trains. Many options have been identified, including membrane processes, granular activated carbon, poweredmore » activated carbon (PAC), enhanced coagulation and/or softening, and alternative disinfectants (e.g., chlorine dioxide, ozone, and chloramines). Of the processes being considered, PAC appears to offer an attractive benefit-to-cost advantage for many water treatment plants, particularly small systems (those serving fewer than 10,000 customers). PAC has traditionally been used by the water treatment industry for the removal of compounds contributing to taste and odor problems. PAC also has the potential to remove naturally occurring organic matter (NOM) from raw waters prior to disinfection, thus controlling the formation of regulated DBPs. Many small water systems are currently using PAC for taste and odor control and have the potential to use PAC for controlling DBPs. Activated carbons can be produced from a variety of raw materials, including wood, peat, coconut husks, and numerous types of coal. The Energy & Environmental Research Center (EERC) has been working on the development of a PAC product to remove NOM from surface water supplies to prevent the formation of carcinogenic DBPs during chlorination. During that study, the sodium and calcium content of the lignites showed a significant effect on the sorption capacity of the activated carbon product. As much as a 130% increase in the humic acid sorption capacity of a PAC produced from a high-sodium-content lignite was observed. We hypothesize that the sodium and calcium content of the coal plays a significant role in the development of pore structures and pore-size distribution, ultimately producing activated carbon products that have greater sorption capacity for specific contaminants, depending on molecular size.« less

Diagnosis of Processes Controlling Dissolved Organic Carbon (DOC) Export in a Subarctic Region by a Dynamic Ecosystem Model

NASA Astrophysics Data System (ADS)

Tang, J.

2015-12-01

Permafrost thawing in high latitudes allows more soil organic carbon (SOC) to become hydrologically accessible. This can increase dissolved organic carbon (DOC) exports and carbon release to the atmosphere as CO2 and CH4, with a positive feedback to regional and global climate warming. However, this portion of carbon loss through DOC export is often neglected in ecosystem models. In this paper, we incorporate a set of DOC-related processes (DOC production, mineralization, diffusion, sorption-desorption and leaching) into an Arctic-enabled version of the dynamic ecosystem model LPJ-GUESS (LPJ-GUESS WHyMe) to mechanistically model the DOC export, and to link this flux to other ecosystem processes. The extended LPJ-GUESS WHyMe with these DOC processes is applied to the Stordalen catchment in northern Sweden. The relative importance of different DOC-related processes for mineral and peatland soils for this region have been explored at both monthly and annual scales based on a detailed variance-based Sobol sensitivity analysis. For mineral soils, the annual DOC export is dominated by DOC fluxes in snowmelt seasons and the peak in spring is related to the runoff passing through top organic rich layers. Two processes, DOC sorption-desorption and production, are found to contribute most to the annual variance in DOC export. For peatland soils, the DOC export during snowmelt seasons is constrained by frozen soils and the processes of DOC production and mineralization, determining the magnitudes of DOC desorption in snowmelt seasons as well as DOC sorption in the rest of months, play the most important role in annual variances of DOC export. Generally, the seasonality of DOC fluxes is closely correlated with runoff seasonality in this region. The current implementation has demonstrated that DOC-related processes in the framework of LPJ-GUESS WHyMe are at an appropriate level of complexity to represent the main mechanism of DOC dynamics in soils. The quantified contributions from different processes on DOC export dynamics could be further linked to the climate change, vegetation composition change and permafrost thawing in this region.

United States Air Force Graduate Student Research Program. Program Technical rept. Volume 2

DTIC Science & Technology

1988-12-01

Applications William Geisler xxiii 13 Stability of Jets Under the Supercritical David Graham State 14 In-Plane Fracture in 2-D Carbon-Carbon Gary Griesheim...Dr. Susan Collins *** Engineering and Services Center 19 Investigation of Sorption Kinetics Mark Brusseau 20 Estimation of Jet Fuel Contamination in...Development 47 A Study of Sky Backgrounds and Sub-Visual Eric Schmidt Cirrus 48 Adaptive Array Architectures with Low- Tien Tran Sensitivity to

Trace metal bioavailability: Modeling chemical and biological interactions of sediment-bound zinc

USGS Publications Warehouse

Luoma, S. N.; Bryan, G.W.; Jenne, Everett A.

1979-01-01

Extractable concentrations of sediment-bound Zn, as modified by the physicochemical form of the metal in the sediments, controlled Zn concentrations in the deposit-feeding bivalvesScrobicularia plana (collected from 40 stations in 17 estuaries in southwest England) andMacoma balthica (from 28 stations in San Francisco Bay). Over a wide range of concentrations, a significant correlation was found between ammonium acetate-soluble concentrations of Zn in sediments and Zn concentrations in Scrobicularia. This correlation was insufficiently precise to be of predictive value for Scrobicularia, and did not hold for Macoma over the narrower range of Zn concentrations observed in San Francisco Bay. Strong correlation of Zn concentrations inScrobicularia and the bioavailability of sediment-bound Zn to Macoma with ratios of sorption substrate (oxides of iron and manganese, organic carbon, carbonates, humic materials) concentrations in sediments were found in both the English and San Francisco Bay study areas. These correlations were attributed to substrate competition for sorption of Zn within sediments, assuming: 1) competition for sorption of Zn was largely controlled by the relative concentrations of substrates present in the sediments and 2) the bioavailability of Zn to the deposit feeders was determined by the partitioning of Zn among the substrates. The correlations indicated that the availability of Zn to the bivalves increased when concentrations of either amorphous inorganic oxides or humic substances increased in sediments. Availability was reduced at increased concentrations of organic carbon and, in San Francisco Bay, ammonium acetate-soluble Mn. Concentrations of biologically available Zn in solution and low salinities may also have enhanced Zn uptake, although the roles of these variables were less obvious from the statistical analysis.

Geochemical processes and the effects of natural organic solutes on the solubility of selenium in coal-mine backfill samples from the Powder River basin, Wyoming

USGS Publications Warehouse

See, R.B.; Reddy, K.J.; Vance, G.F.; Fadlelmawla, A.A.; Blaylock, M.J.

1995-01-01

Geochemical processes and the effects of natural organic solutes on the solubility of selenium in coal-mine backfill aquifers were investigated. Backfill and ground-water samples were collected at coal mines in the Powder River Basin, Wyoming. Backfill was generally dominated by aluminum (14,400 to 49,000 mg/kg (milligrams per kilogram)), iron (3,330 to 23,200 mg/kg), and potassium (7,950 to 18,000 mg/kg). Backfill saturated-paste selenium concentrations ranged from 1 to 156 mg/kg (microsiemens per kilogram). Ground-water total selenium concentrations ranged from 3 to 125 mg/L. Dissolved organic carbon in all ground-water samples was dominated by hydrophobic and hydrophilic acids (38 to 84 percent). Selenite sorption/desorption experiments were conducted using background solutions of distilled-deionized water, 0.1 molar calcium chloride, and isolated hydrophobic and hydrophilic acids. Selenite sorption was larger when 0.1 molar calcium chloride was used. The addition of hydrophilic acid decreased selenite sorption more than the addition of hydrophobic acids. Geochemical modelling was used to predict the solid phases controlling dissolved selenium concentrations and to evaluate the effects of dissolved organic carbon on selenium solubility. Results suggested that 55 to 90 percent of selenium in backfill precipitation/dissolution extracts was dominated by magnesium selenate ion pairs. Dissolved organic carbon had little effect on selenium speciation. A redox chamber was constructed to control Eh and pH in water and backfill-core sample suspensions. The response of selenite and selenate in water samples to redox conditions did not follow thermodynamic predictions. Reduction of selenate in water samples did not occur at any of the redox levels tested.

REVISED GUIDELINES FOR USING CELLULOSE DEGRADATION PRODUCT-IMPACTED KD VALUES FOR PERFORMANCE ASSESSMENTS AND COMPOSITE ANALYSES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kaplan, D.

2012-05-14

Cellulosic materials include wood, paper, rags, and cardboard products. These materials are co-disposed with radiological waste at the Savannah River Site's (SRS) E-Area Low-Level Waste Facility (ELLWF). Cellulosic materials readily degrade in the environment to form cellulose degradation products (CDP) that will partition to the sediment or remain mobile in the groundwater. Savannah River National Lab (SRNL) has conducted studies to estimate the impact of CDP on radionuclide sorption to SRS sediments (Kd values). It was found that CDP impact on radionuclide sorption varies with radionuclide and CDP concentration. Furthermore, it was found that the amount of carbon (C) inmore » the system could increase or decrease Kd values with respect to the base case of when no CDP was added. Throughout the expected pH range of the ELLWF, a low concentration of CDP in the system would increase Kd values (because C would sorb to the sediment and provide more exchange sites for radionuclides to sorb), whereas greater concentrations of CDP ({ge}20 mg/L C) would decrease Kd values (because C would remain in solution and complex the radionuclide and not permit the radionuclide to sorb to the sediment). A review of >230 dissolved organic carbon (DOC) groundwater concentrations in the Old Radioactive Waste Burial Ground (ORWBG) at the SRS indicated that the average DOC concentration, a gross measure of CDP, was 5 mg/L C. At approximately this DOC concentration, the laboratory studies demonstrated that no anions (Tc, I, or Se) or cations (Ni, Sr, Ce, Eu, Zr, or Th) have decreased sorption in the presence of carbon (an analogue for CDP).« less

Contribution of hydrophobic effect to the sorption of phenanthrene, 9-phenanthrol and 9, 10-phenanthrenequinone on carbon nanotubes.

PubMed

Peng, Hongbo; Zhang, Di; Pan, Bo; Peng, Jinhui

2017-02-01

Polycyclic aromatic hydrocarbons (PAHs), with diverse sources and acute toxicity, are categorized as priority pollutants. Previous studies have stated that the hydrophobic effect controls PAH sorption, but no study has been conducted to quantify the exact contribution of the hydrophobic effect. Considering the well-defined structure of carbon nanotubes and their stable chemical composition in organic solvents, three multi-walled carbon nanotubes (MWCNTs) were selected as a model adsorbent. Phenanthrene (PHE) and its degradation intermediates 9-phenanthrol (PTR) and 9, 10-phenanthrenequinone (PQN) were used as model adsorbates. To quantify the contribution of the hydrophobic effect for these three chemicals, the effect of organic solvent (methanol and hexadecane) was investigated. Adsorption isotherms for PHE, PTR and PQN were well fitted by the Freundlich isotherm model. A positive relationship between adsorption affinities of these three chemicals and specific surface area (SSA) was observed in hexadecane but not in water or methanol. Other factors should be included other than SSA. Adsorption of PQN on MWCNTs with oxygen functional groups was higher than that on pristine MWCNTs due to π-π EDA interactions. The contribution of hydrophobic effect was 50%-85% for PHE, suggesting that hydrophobic effect was the predominant mechanism. This contribution was lower than 30% for PTR/PQN on functionalized MWCNTs. Hydrogen bonds control the adsorption of PTR, and π-π bonding interactions control PQN sorption after screening out the hydrophobic effect in hexadecane. Hydrophobic effect is the control mechanism for nonpolar chemicals, while functional groups of CNTs and solvent types control the adsorption of polar compounds. Extended work on quantifying the relationship between chemical structure and the contribution of the hydrophobic effect will provide a useful technique for PAH fate modeling. Copyright © 2016 Elsevier Ltd. All rights reserved.

Competitive sorption of organic contaminants in chalk.

PubMed

Graber, E R; Borisover, M

2003-12-01

In the Negev desert, Israel, a chemical industrial complex is located over fractured Eocene chalk formations where transfer of water and solutes between fracture voids and matrix pores affects migration of contaminants in the fractures due to diffusion into the chalk matrix. This study tests sorption and sorption competition between contaminants in the chalk matrix to make it possible to evaluate the potential for contaminant attenuation during transport in fractures. Single solute sorption isotherms on chalk matrix material for five common contaminants (m-xylene, ametryn, 1,2-dichloroethane, phenanthrene, and 2,4,6-tribromophenol) were found to be nonlinear, as confirmed in plots of Kd versus initial solution concentration. Over the studied concentration ranges, m-xylene Kd varied by more than a factor of 100, ametryn Kd by a factor of 4, 1,2-dichloroethane Kd by more than a factor of 3, phenanthrene Kd by about a factor of 2, and 2,4,6-tribromophenol Kd by a factor of 10. It was earlier found that sorption is to the organic matter component of the chalk matrix and not to the mineral phases (Chemosphere 44 (2001) 1121). Nonlinear sorption isotherms indicate that there is at least some finite sorption domain. Bi-solute competition experiments with 2,4,6-tribromophenol as the competitor were designed to explore the nature of the finite sorption domain. All of the isotherms in the bi-solute experiments are more linear than in the single solute experiments, as confirmed by smaller variations in Kd as a function of initial solution concentration. For both m-xylene and ametryn, there is a small nonlinear component or domain that was apparently not susceptible to competition by 2,4,6-tribromophenol. The nonlinear sorption domain(s) is best expressed at low solution concentrations. Inert-solvent-normalized single and bi-solute sorption isotherms demonstrate that ametryn undergoes specific force interactions with the chalk sorbent. The volume percent of phenanthrene sorbed at the liquid solubility limit is calculated to be 13% v:v in both the single and bi-solute experiments. This value exceeds what may be reasonably interpreted as partitioning of phenanthrene into organic matter, despite the relative linearity of the phenanthrene sorption isotherm (compared with other compounds) in both single and bi-solute systems.

MERCURY CAPTURE ON COAL COMBUSTION FLY ASH. (R827649)

EPA Science Inventory

A study was performed at the Energy and Environmental Research Center (EERC) to test the hypotheses that (1) different carbon types contained in coal combustion fly ash have variable sorption capabilities relative to mercury and (2) the inorganic fraction of coal combustion fl...

Detection of Singlet Oxygen Formation inside Photoactive Biohybrid Composite Material.

PubMed

Hajdu, Kata; Ur Rehman, Ateeq; Vass, Imre; Nagy, László

2017-12-26

Photosynthetic reaction center proteins (RCs) are the most efficient light energy converter systems in nature. The first steps of the primary charge separation in photosynthesis take place in these proteins. Due to their unique properties, combining RCs with nano-structures promising applications can be predicted in optoelectronic systems. In the present work RCs purified from Rhodobacter sphaeroides purple bacteria were immobilized on multiwalled carbon nanotubes (CNTs). Carboxyl-and amine-functionalised CNTs were used, so different binding procedures, physical sorption and chemical sorption as well, could be applied as immobilization techniques. Light-induced singlet oxygen production was measured in the prepared photoactive biocomposites in water-based suspension by histidine mediated chemical trapping. Carbon nanotubes were applied under different conditions in order to understand their role in the equilibration of singlet oxygen concentration in the suspension. CNTs acted as effective quenchers of ¹O₂ either by physical (resonance) energy transfer or by chemical (oxidation) reaction and their efficiency showed dependence on the diffusion distance of ¹O₂.

25th anniversary article: "Cooking carbon with salt": carbon materials and carbonaceous frameworks from ionic liquids and poly(ionic liquid)s.

PubMed

Fellinger, Tim-Patrick; Thomas, Arne; Yuan, Jiayin; Antonietti, Markus

2013-11-06

This review surveys recent work on the use of ionic liquids (ILs) and polymerized ionic liquids (PILs) as precursors to synthesize functional carbon materials. As solvents or educts with negligible vapour pressure, these systems enable simple processing, composition, and structural control of the resulting carbons under rather simple and green synthesis conditions. Recent applications of the resulting nanocarbons across a multitude of fields, such as fuel cells, energy storage in batteries and supercapacitors, catalysis, separation, and sorption materials are highlighted. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Development of a sorption rate technique for single zeolite crystals using an electrodynamic balance

NASA Astrophysics Data System (ADS)

Welegala, Mark Joseph

Conventional means for evaluating intracrystalline diffusion in zeolites are complicated by extracrystalline mass transport resistances, crystallite size distribution, sorption heat effects, and finite instrument response times. A potentially direct means of overcoming these problems is to study sorption uptake on a single crystal suspended within a flowing gas stream in an electrodynamic balance (EDB). The objectives of this research were to design, build and investigate the viability of using such a device for obtaining diffusion coefficients from simple sorbate/zeolite systems, by computing the sorption uptake curve from the levitation voltage as a function of time. The initial electronic cell design was strongly influenced by flow mixing considerations. Accordingly, the conventional bihyperboloid electrode configuration was discarded in favor of novel four-ring (4R), and later two-ring/two-screen (2R/2S) designs with cylindrical interior geometries. A detailed numerical model based on the Method of Discrete Charges (MDC) was developed and used to aid in the design and operational understanding of these cells. Several 2R/2S designs were built and tested, including teflon/mica composite and ceramic cells capable of withstanding up to 750oF, for in situ activation of the zeolites. The diffusion of carbon dioxide in zeolite A was selected for testing due to the large differential weight change (10-20%) which occurs at ambient conditions and the availability of reliable experimental diffusion results (Yucel and Ruthven, 1980a). In addition to the carbon dioxide sorbate, water on zeolite 4A and a system relatively immune to atmospheric contamination, CO2 on activated carbon were also studied. Laboratory 4A crystals of up to 45 μm were grown using Charnell's method. These large solid particles were captured using a dry charging technique, and held during elevated temperature dehydration. Preliminary experimentation introduced externally dried crystals to the cell chamber in 0.5-3 minutes. Only minimal desorption results with carbon dioxide and later, adsorption for water vapor, were obtained. Further experiments revealed that crystal contamination from laboratory air can be considerable in less than one minute, thereby preadsorbing airborne water vapor. The experimental methodology was changed to include in situ heating. Subsequent attempts to circumvent laser heating of the particle had limited success. Particle loss, (due to excessive charge loss) and cell material degradation limited the process to null point temperatures of approximately 260oC, which is insufficient for complete zeolite dehydration. Early, it was demonstrated that gas compositions could be switched while flowing without losing the particle. However, the resulting concentration transient imposes an ultimate limitation on the technique for application to rapidly diffusing systems. Also, the fact that the technique is gravimetric requires that the diffusing species must be appreciably adsorbed at ambient conditions. Thus the single crystal sorption apparatus based on the electrodynamic containment device would appear to have use primarily for strongly adsorbed and slowly diffusing species. (Abstract shortened by UMI.)

Response surface methodology optimization for sorption of malachite green dye on sugarcane bagasse biochar and evaluating the residual dye for phyto and cytogenotoxicity.

PubMed

Vyavahare, Govind D; Gurav, Ranjit G; Jadhav, Pooja P; Patil, Ravishankar R; Aware, Chetan B; Jadhav, Jyoti P

2018-03-01

In the present study, sorption and detoxification of malachite green (MG) dye was executed using biochar resulting after pyrolysis of agro-industrial waste at 400, 600 and 800 °C. Maximum sorption of MG dye (3000 mg/L) was observed on the sugarcane bagasse biochar (SCB) prepared at 800 °C. The interactive effects of different factors like dye concentration, time, pH and temperature on sorption of MG dye were investigated using response surface methodology (RSM). Optimum MG dye concentration, contact time, temperature and pH predicted through Box-Behnken based RSM model were 3000 mg/L MG dye, 51.89 min, 60 °C and 7.5, respectively. ANOVA analysis displayed the non-significant lack of fit value (0.4566), whereas, the predicted correlation coefficient values (R 2 0.8494) were reasonably in agreement with the adjusted value (R 2 0.9363) demonstrating highly significant model for MG dye sorption. The applicability of this model was also checked through F- test (30.39) with lower probability (0.0001) value. Furthermore, the characterization of SCB was performed using fourier transform infra-red spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscope (SEM), Brunauer-Emmett-Teller surfaces (BET), total organic carbon (TOC) and atomic absorption spectroscopy (AAS). Phyto-toxicity and cytogenotoxicity studies showed successful removal of MG dye using SCB. In addition, the batch sorption studies for reutilization of SCB revealed that the SCB was effective in removal of MG for five repeated cycles. This technology would be effective for treating the toxic textile effluent released from the textile industries. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorption of Perfluorinated Compounds onto different types of sewage sludge and assessment of its importance during wastewater treatment.

PubMed

Arvaniti, Olga S; Andersen, Henrik R; Thomaidis, Nikolaos S; Stasinakis, Athanasios S

2014-09-01

The distribution coefficient (Kd) and the organic carbon distribution coefficient (KOC) were determined for four Perfluorinated Compounds (PFCs) to three different types of sludge taken from a conventional Sewage Treatment Plant (STP). Batch experiments were performed in six different environmental relevant concentrations (200ngL(-1)to 5μgL(-1)) containing 1gL(-1) sludge. Kd values ranged from 330 to 6015, 329 to 17432 and 162 to 11770Lkg(-1) for primary, secondary and digested sludge, respectively. The effects of solution's pH, ionic strength and cation types on PFCs sorption were also evaluated. Sorption capacities of PFCs significantly decreased with increased pH values from 6 to 8. Furthermore, the divalent cation (Ca(2+)) enhanced PFCs sorption to a higher degree in comparison with the monovalent cation (Na(+)) at the same ionic strength. The obtained Kd values were applied to estimate the sorbed fractions of each PFC in different stages of a typical STP and to calculate their removal through treated wastewater and sludge. In primary settling tank, the predicted sorbed fractions ranged from 3% for Perfluorooctanoic Acid (PFOA) to 55% for Perfluoroundecanoic acid (PFUdA), while in activated sludge tank and anaerobic digester sorption was more than 50% for all target compounds. Almost 86% of initial PFOA load is expected to be detected in treated wastewater; while Perfluorodecanoic acid (PFDA), PFUdA and Perfluorooctanesulfonate (PFOS) can be significantly removed (>49%) via sorption to primary and excess secondary sludge. In anaerobic digester, the major part (>76%) of target PFCs is expected to be sorbed to sludge, while almost 3% of initial PFOA load will be detected in sludge leachates. Copyright © 2014 Elsevier Ltd. All rights reserved.

Role of soil sorption and microbial degradation on dissipation of mesotrione in plant-available soil water.

PubMed

Shaner, Dale; Brunk, Galen; Nissen, Scott; Westra, Phil; Chen, Wenlin

2012-01-01

Mesotrione is a carotenoid biosynthesis-inhibiting herbicide labeled for pre-emergence and postemergence weed control in corn production. Understanding the factors that influence the dissipation of mesotrione in soil and in the plant-available water (PAW) is important for the environmental fate assessment and optimal weed management practices. The present research investigated the role of soil properties and microbial activities on the interrelated sorption and degradation processes of mesotrione in four soils by direct measurements of PAW. We found that mesotrione bound to the soils time dependently, with approximately 14 d to reach equilibrium. The 24-h batch-slurry equilibrium experiments provided the sorption partition coefficient ranging from 0.26 to 3.53 L kg(-1), depending on soil organic carbon and pH. The dissipation of mesotrione in the soil-bound phase was primarily attributed to desorption to the PAW. Degradation in the PAW was rapid and primarily dependent on microbial actions, with half-degradation time (DT(50)) <3 d in all four soils tested. The rapid degradation in the PAW became rate limited by sorption as more available molecules were depleted in the soil pore water, resulting in a more slowed overall process for the total soil-water system (DT(50) <26 d). The dissipation of mesotrione in the PAW was due to microbial metabolism and time-dependent sorption to the soils. A coupled kinetics model calibrated with the data from the laboratory centrifugation technique provided an effective approach to investigate the interrelated processes of sorption and degradation in realistic soil moisture conditions. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Evaluating the sorption of organophosphate esters to different sourced humic acids and its effects on the toxicity to Daphnia magna.

PubMed

Pang, Long; Liu, Jingfu; Yin, Yongguang; Shen, Mohai

2013-12-01

Because of large usage as flame retardants and additives, organophosphate esters (OPEs) are widely detected in the environment and regarded as emerging contaminants. However, the sorption of OPEs to organic matter and its effects have scarcely been studied. In the present study, the sorption of 9 commonly used OPEs to 4 representative humic acids--Elliott Soil humic acid, Suwannee River humic acid, Aldrich humic acid, and Acros humic acid--in the range of 0 mg/L to 50 mg/L dissolved organic carbon (DOC), was evaluated with negligible-depletion solid-phase microextraction and verified by its impacts on the toxicity to the aquatic invertebrate Daphnia magna. Whereas OPEs with a high octanol/water partition coefficient (log K(OW)=4.51-6.64) were associated with humic acids mainly by hydrophobic interaction with DOC partition coefficient (K(DOC)) in the range of 10²·²² to 10⁵·³¹, the sorption of low-K(OW) OPEs (log K(OW)=-0.65 to 2.59) to humic acids was not hydrophobic interaction-dominant, with K(DOC) in the range of 10³·⁴⁷ to 10⁴·²⁹. These results were corroborated by the effects of humic acids on the acute toxicity of 3 high-K(OW) OPEs to D. magna. The sorption of OPEs to Suwannee River humic acid was weak and had negligible effects on the toxicity of high-K(OW) OPEs; the presence of terrestrial Acros humic acid (50 mg/L DOC), however, significantly decreased the toxicity by 53% to 60%. The results indicated that the strong sorption between high-K(OW) OPEs and terrestrial humic acid might affect their transportation and bioavailability. © 2013 SETAC.

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

USGS Publications Warehouse

Davis, J.A.; Fuller, C.C.; Cook, A.D.

1987-01-01

The rate of Cd2+ sorption by calcite was determined as a function of pH and Mg2+ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO3. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca2+ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd2+ sorption decrease with increasing pH or with increasing Mg2+. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer. A model is presented which is consistent with the rates of Cd2+ sorption and Ca2+ isotopic exchange. In the model, the first step in Cd2+ sorption involves a fast adsorption reaction that is followed by diffusion of Cd2+ into a surface layer of hydrated CaCO3 that overlies crystalline calcite. Desorption of Cd2+ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO3, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution. ?? 1987.

Chloropicrin emission reduction by soil amendment with biochar

USDA-ARS?s Scientific Manuscript database

Biochar is the carbon-enriched and porous material produced by heating organic material under conditions of limited or no oxygen. As biochar has a large surface area and strong sorption capacity, it can enhance the sequestration of organic contaminants such as pesticides in soil. Chloropicrin (CP) i...

Biochar as a sorbent for chlorinated hydrocarbons - sorption and extraction experiments in single and bi-solute systems

NASA Astrophysics Data System (ADS)

Schreiter, I. J.; Wefer-Roehl, A.; Graber, E. R.; Schueth, C.

2016-12-01

Biochar (BC) is increasingly deemed a potential sorbent for contaminants in soil and water remediation, and brownfield restoration. In this study, sorption and extraction experiments were performed to assess the potential of three different BCs to sorb and retain the chlorinated hydrocarbons TCE and PCE. BCs studied were produced from wood chips, grain husk, and cattle manure at 450 °C. A commercially available activated carbon (AC) served as a reference. The sorption behaviour was studied in batch experiments in single solute and bi-solute systems. Resulting isotherms were fitted to the Freundlich model. To assess the desorption behaviour, a five step extraction scheme (water at 40°C, water at 80°C, methanol at 50°C, toluene at 50°C, and n-hexane at 50°) was developed utilizing Accelerated Solvent Extraction. Isotherms revealed distinct differences in sorption behaviour depending on BC feedstock. Sorption capacity ranked as follows: wood chip BC > grain husk BC > cattle manure BC for both contaminants. This sequence could be attributable to an increasing specific surface area and a decreasing ash content of the sorbents. It is noteworthy that all three BCs were more effective in adsorbing TCE, which is surprising, given the higher logKOWof PCE. The reverse trend was observed for the AC. In bi-solute experiments, PCE sorbed as good as or stronger than TCE, yet the total mass of sorbed compounds was higher. In contrast, AC showed a significant decrease of TCE sorption. Extraction experiments revealed that for all BCs a large fraction of the contaminants could not be readily desorbed. In all cases, water remobilized < 5 % of the total contaminant mass and up to 70 % could not be extracted by any of the solvents. The findings suggest that BC is a promising sorbent for mixed contaminant systems as it offers a diverse nature of sorption sites and is more effective in long-term stabilization than AC.

Polar and aliphatic domains regulate sorption of phthalic acid esters (PAEs) to biochars.

PubMed

Sun, Ke; Jin, Jie; Keiluweit, Marco; Kleber, Markus; Wang, Ziying; Pan, Zezhen; Xing, Baoshan

2012-08-01

Molecular variations among different biochar categories translate into differences in their ability to function as sorbents to three phthalic acid esters (PAEs) representing a gradient in hydrophobicity. The sorption capacity (K(OC)) for all three PAEs was the greatest for amorphous biochars (heat treatment temperature HTT=400 °C), followed by biochars produced at 300 °C, and was best explained by the hydrophobicity of the sorbate. Greater alkyl C content and higher polarity of grass chars versus wood chars prepared at similar temperatures explained both (a) the difference in sorbent strength between feedstocks and (b) the maximum in sorbent strength at relatively low HTTs (300-400 °C). Hydrophobic partitioning into 'soft' alkyl carbon and specific H-bonding involving char-bound O and N groups jointly account for high affinities of PAEs for low-HTT biochars. The results highlight the influence of feedstocks and HTTs on PAEs sorption strength and mechanism. Copyright © 2012 Elsevier Ltd. All rights reserved.

Sorption of diclofenac and naproxen onto MWCNT in model wastewater treated by H2O2 and/or UV.

PubMed

Czech, Bożena; Oleszczuk, Patryk

2016-04-01

The application of oxidation processes such as UV and/or H2O2 will change the physicochemical properties of carbon nanotubes (CNT). It may affect the sorption affinity of CNT to different contaminants and then affect their fate in the environment. In the present study the adsorption of two very common used pharmaceuticals (diclofenac and naproxen) onto CNT treated by UV, H2O2 or UV/H2O2 was investigated. Four different adsorption models (Freundlich, Langmuir, Temkin, Dubinin-Radushkevich) were tested. The best fitting of experimental data was observed for Freundlich or Langmuir model. The significant relationships between Q calculated from Langmuir model with O% and dispersity were observed. Kinetics of diclofenac and naproxen followed mainly pseudo-second order indicating for chemisorption limiting step of adsorption. The data showed that the mechanism of sorption was physical or chemical depending on the type of CNT modification. Copyright © 2015 Elsevier Ltd. All rights reserved.

Pedotransfer functions for isoproturon sorption on soils and vadose zone materials.

PubMed

Moeys, Julien; Bergheaud, Valérie; Coquet, Yves

2011-10-01

Sorption coefficients (the linear K(D) or the non-linear K(F) and N(F)) are critical parameters in models of pesticide transport to groundwater or surface water. In this work, a dataset of isoproturon sorption coefficients and corresponding soil properties (264 K(D) and 55 K(F)) was compiled, and pedotransfer functions were built for predicting isoproturon sorption in soils and vadose zone materials. These were benchmarked against various other prediction methods. The results show that the organic carbon content (OC) and pH are the two main soil properties influencing isoproturon K(D) . The pedotransfer function is K(D) = 1.7822 + 0.0162 OC(1.5) - 0.1958 pH (K(D) in L kg(-1) and OC in g kg(-1)). For low-OC soils (OC < 6.15 g kg(-1)), clay and pH are most influential. The pedotransfer function is then K(D) = 0.9980 + 0.0002 clay - 0.0990 pH (clay in g kg(-1)). Benchmarking K(D) estimations showed that functions calibrated on more specific subsets of the data perform better on these subsets than functions calibrated on larger subsets. Predicting isoproturon sorption in soils in unsampled locations should rely, whenever possible, and by order of preference, on (a) site- or soil-specific pedotransfer functions, (b) pedotransfer functions calibrated on a large dataset, (c) K(OC) values calculated on a large dataset or (d) K(OC) values taken from existing pesticide properties databases. Copyright © 2011 Society of Chemical Industry.

Sorption of citalopram, irbesartan and fexofenadine in soils: Estimation of sorption coefficients from soil properties.

PubMed

Klement, Aleš; Kodešová, Radka; Bauerová, Martina; Golovko, Oksana; Kočárek, Martin; Fér, Miroslav; Koba, Olga; Nikodem, Antonín; Grabic, Roman

2018-03-01

The sorption of 3 pharmaceuticals, which may exist in 4 different forms depending on the solution pH (irbesartan in cationic, neutral and anionic, fexofenadine in cationic, zwitter-ionic and anionic, and citalopram cationic and neutral), in seven different soils was studied. The measured sorption isotherms were described by Freundlich equations, and the sorption coefficients, K F (for the fixed n exponent for each compound), were related to the soil properties to derive relationships for estimating the sorption coefficients from the soil properties (i.e., pedotransfer rules). The largest sorption was obtained for citalopram (average K F value for n = 1 was 1838 cm 3  g -1 ) followed by fexofenadine (K F  = 35.1 cm 3/n μg 1-1/n g -1 , n = 1.19) and irbesartan (K F  = 3.96 cm 3/n μg 1-1/n g -1 , n = 1.10). The behavior of citalopram (CIT) in soils was different than the behaviors of irbesartan (IRB) and fexofenadine (FEX). Different trends were documented according to the correlation coefficients between the K F values for different compounds (R IRB,FEX  = 0.895, p-value<0.01; R IRB,CIT  = -0.835, p-value<0.05; R FEX,CIT  = -0.759, p-value<0.05) and by the reverse relationships between the K F values and soil properties in the pedotransfer functions. While the K F value for citalopram was positively related to base cation saturation (BCS) or sorption complex saturation (SCS) and negatively correlated to the organic carbon content (Cox), the K F values of irbesartan and fexofenadine were negatively related to BCS, SCS or the clay content and positively related to Cox. The best estimates were obtained by combining BCS and Cox for citalopram (R 2  = 93.4), SCS and Cox for irbesartan (R 2  = 96.3), and clay content and Cox for fexofenadine (R 2  = 82.9). Copyright © 2017 Elsevier Ltd. All rights reserved.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paajanen, A.; Lehto, J.; Santapakka, T.

The efficiencies of 15 commercially available activated carbons were tested for the separation of trace cobalt ({sup 60}Co) in buffer solutions at pH 5.0, 6.7, and 9.1. On the basis of the results four carbon products, Diahope-006, Eurocarb TN5, Hydraffin DG47, and Norit ROW Supra, were selected for further study. These carbons represented varying (low, medium and high) cobalt removal efficiencies and were prepared of three typical raw materials: peat, coconut shell, or coal. Study was made of the effects on sorption efficiencies of factors of interest in metal/radionuclide-bearing waste effluents. These factors were pH, sodium ions, borate, and citrate.

Controlling parameters of fluorescent tracer sorption on soils and sediments

NASA Astrophysics Data System (ADS)

Bork, Marcus; Graf-Rosenfellner, Markus; Lange, Jens; Lang, Friederike

2017-04-01

Fluorescent dyes like uranine (UR) and sulforhodamine B (SRB) have been widely used, especially for tracing hydrological processes. In the recent past, efforts have intensified to use fluorescent tracers also in soils, for example as proxies for organic pollutants. However, the sorption properties of both organic pollutants and fluorescent tracers have to be exactly known to succeed. Yet existing knowledge for soils is still incomplete and poorly standardized. For this reason, we carried out laboratory batch experiments to determine sorption isotherms of UR and SRB with varying pH, soil texture and organic carbon content (OC). As sorbents we used a sandy sediment with low OC, a silty loamy topsoil with 2.8 %-OC and a similar textured subsoil containing 0.6 %-OC. For both tracers six concentration steps each were prepared and shaken with the suspended sorbent for 42 h using a sorbent:solution ratio of 1:5. During the equilibration, the pH was repeatedly adjusted to 5.5, 6.5, and 7.5 by adding hydrochloric acid (HCl) or sodium hydroxide (NaOH). Subsequently, the tracer-sorbent-suspension was centrifuged and the fluorescence of the tracer in the supernatant was measured. In order to examine the influence of OC and the clay fraction on the tracer sorption, batch-experiments at pH 7.5 were also conducted with manipulated sorbents: top- and subsoil samples were treated with H2O2 to remove organic matter and the clay mineral montmorillonite was added to the sandy sediment to achieve final clay contents of 0.1 %, 0.5 %, 1 %, 2 %, 2.5 %, 5 % and 10 % clay. We observed a negative relationship between the linear sorption coefficient Kd and pH, which was stronger for UR than for SRB. Increasing numbers of negative sorption sites and functional groups of both tracers and sorbents with increasing pH might be the reason for this observation. Besides the pH-value, quantity and quality of clay and OC had a crucial influence on the sorption of UR and SRB in soils and sediment. As expected, increasing clay content, which is associated with an increasing specific surface and therefore more sorption sites, led to an increasing sorption of UR and SRB. Here, after the addition of 4 % of the clay mineral montmorillonite, nearly 100 % of both tracers were sorbed. Furthermore, OC influenced the sorption of UR and SRB in different ways: while the sorption of UR increased, the sorption of SRB decreased with increasing OC. In conclusion, the sorption behaviour of the fluorescent tracers UR and SRB in soils is very complex, and for appropriate application, the physico-chemical properties of the respective soils or sediments have to be considered. These conditions essentially determine if the respective tracer shows a conservative or non-conservative behaviour. With these aspects in mind, applying SRB and UR has the potential to be a cheap and fast method to estimate the fate of pollutants in soils or sediments.

Molecular hydrogen sorption capacity of D-shwarzites

NASA Astrophysics Data System (ADS)

Krasnov, Pavel O.; Shkaberina, Guzel S.; Kuzubov, Alexander A.; Kovaleva, Evgenia A.

2017-09-01

Schwarzites are one of the most well-known forms of nanoporous carbon. High porosity and large surface area of these materials make them promising candidates for molecular hydrogen storage. Quantum-chemical modeling showed that hydrogen weight fraction inside D-schwarzite structure depends on the number of atoms per unit cell that determines its size and morphology. D480 schwarzite has demonstrated the largest value of hydrogen sorption capacity amongst the structures considered in this work. It reaches 7.65% at the technologically acceptable values of temperature and pressure (300 K and 10 MPa). Though being lower than that required by DOE (9%), this amount can be increased by using schwarzites with larger unit cell corresponding to the larger surface area.

Effect of organic carbon on sorption of human adenovirus to soil particles and laboratory containers

EPA Science Inventory

A key factor controlling the relationship between virus release and human exposure is how virus particles interact with soils, sediments and other solid particles in the environment and in engineered treatment systems. Finding no previous investigations of human adenovirus (HAdV)...

Engineered carbon (biochar) prepared by direct pyrolysis of Mg-accumulated tomato tissues: Characterization and phosphate removal potential

USDA-ARS?s Scientific Manuscript database

An innovative synthesis was developed to produce engineered biochar from magnesium (Mg) enriched tomato tissues through slow pyrolysis in a N2 environment. The resulting Mg-biochar composites showed excellent sorption ability to phosphate in aqueous solutions. The engineered biochar contained nanosc...

Stabilization of lead and copper by biochar amendments in arms range soils: Influence of biochar characteristics, soil property, and equilibrium conditions

USDA-ARS?s Scientific Manuscript database

Soil amendment of char products (biochar) from thermochemical processing (slow/fast pyrolysis and gasification) of biomass for biofuel production has received considerable interests for contaminant sorption, soil fertilization, and carbon sequestration. Of potential sites for biochar application, h...

Evaluation of theoretical and empirical water vapor sorption isotherm models for soils

NASA Astrophysics Data System (ADS)

Arthur, Emmanuel; Tuller, Markus; Moldrup, Per; de Jonge, Lis W.

2016-01-01

The mathematical characterization of water vapor sorption isotherms of soils is crucial for modeling processes such as volatilization of pesticides and diffusive and convective water vapor transport. Although numerous physically based and empirical models were previously proposed to describe sorption isotherms of building materials, food, and other industrial products, knowledge about the applicability of these functions for soils is noticeably lacking. We present an evaluation of nine models for characterizing adsorption/desorption isotherms for a water activity range from 0.03 to 0.93 based on measured data of 207 soils with widely varying textures, organic carbon contents, and clay mineralogy. In addition, the potential applicability of the models for prediction of sorption isotherms from known clay content was investigated. While in general, all investigated models described measured adsorption and desorption isotherms reasonably well, distinct differences were observed between physical and empirical models and due to the different degrees of freedom of the model equations. There were also considerable differences in model performance for adsorption and desorption data. While regression analysis relating model parameters and clay content and subsequent model application for prediction of measured isotherms showed promise for the majority of investigated soils, for soils with distinct kaolinitic and smectitic clay mineralogy predicted isotherms did not closely match the measurements.

Sequestration of hydrophobic organic contaminants by geosorbents

USGS Publications Warehouse

Luthy, Richard G.; Aiken, George R.; Brusseau, Mark L.; Cunningham, Scott D.; Gschwend, Philip M.; Pignatello, Joseph J.; Reinhard, Martin; Traina, Samuel J.; Weber, Walter J.; Westall, John C.

1997-01-01

The chemical interactions of hydrophobic organic contaminants (HOCs) with soils and sediments (geosorbents) may result in strong binding and slow subsequent release rates that significantly affect remediation rates and endpoints. The underlying physical and chemical phenomena potentially responsible for this apparent sequestration of HOCs by geosorbents are not well understood. This challenges our concepts for assessing exposure and toxicity and for setting environmental quality criteria. Currently there are no direct observational data revealing the molecular-scale locations in which nonpolar organic compounds accumulate when associated with natural soils or sediments. Hence macroscopic observations are used to make inferences about sorption mechanisms and the chemical factors affecting the sequestration of HOCs by geosorbents. Recent observations suggest that HOC interactions with geosorbents comprise different inorganic and organic surfaces and matrices, and distinctions may be drawn along these lines, particularly with regard to the roles of inorganic micropores, natural sorbent organic matter components, combustion residue particulate carbon, and spilled organic liquids. Certain manipulations of sorbates or sorbent media may help reveal sorption mechanisms, but mixed sorption phenomena complicate the interpretation of macroscopic data regarding diffusion of HOCs into and out of different matrices and the hysteretic sorption and aging effects commonly observed for geosorbents. Analytical characterizations at the microscale, and mechanistic models derived therefrom, are needed to advance scientific knowledge of HOC sequestration, release, and environmental risk.

Sorption of Poly- and Perfluoroalkyl Substances (PFASs) Relevant to Aqueous Film-Forming Foam (AFFF)-Impacted Groundwater by Biochars and Activated Carbon.

PubMed

Xiao, Xin; Ulrich, Bridget A; Chen, Baoliang; Higgins, Christopher P

2017-06-06

Despite growing concerns about human exposure to perfluorooctanoate (PFOA) and perfluorooctanesulfonate (PFOS), other poly- and perfluoroalkyl substances (PFASs) derived from aqueous film-forming foams (AFFFs) have garnered little attention. While these other PFASs may also be present in AFFF-impacted drinking water, their removal by conventional drinking-water treatment is poorly understood. This study compared the removal of 30 PFASs, including 13 recently discovered PFASs, from an AFFF-impacted drinking water using carbonaceous sorbents (i.e., granular activated carbon, GAC). The approach combined laboratory batch experiments and modeling: batch sorption data were used to determine partition coefficients (K d ) and calibrate a transport model based on intraparticle diffusion-limited sorption kinetics, which was used to make forward predictions of PFAS breakthrough during GAC adsorption. While strong retention was predicted for PFOS and PFOA, nearly all of the recently discovered polyfluorinated chemicals and PFOS-like PFASs detected in the AFFF-impacted drinking water were predicted to break through GAC systems before both PFOS and PFOA. These model breakthrough results were used to evaluate a simplified approach to predicting PFAS removal by GAC using compound-specific retention times on a C18 column (RT C18 ). Overall, this study reveals that GAC systems for the treatment of AFFF-impacted sources of water for PFOA and PFOS likely achieve poor removal, when operated only for the treatment of PFOS and PFOA, of many unmonitored PFASs of unknown toxicity.

Synthesis, characterization and study of sorption parameters of multi-walled carbon nanotubes/chitosan nanocomposite for the removal of picric acid from aqueous solutions.

PubMed

Khakpour, Roghayeh; Tahermansouri, Hasan

2018-04-01

The modification of carboxylated multi-wall carbon nanotubes (MWCNT-COOH) with chitosan (Chi) has been investigated to prepare a nanocomposite material (MWCNT-Chi) for the removal of picric acid from aqueous solutions. Materials were characterized by FT-IR, TGA, DTG, FESEM, EDX, BET and zeta potential. Batch experiments such as solution pH, dosage of adsorbents, contact time, concentration of the picric acid and temperature were achieved to study sorption process. Kinetic studies were well described by pseudo-second-order kinetic model for both adsorbents. The six isotherm models: Langmuir (four linear forms), Freundlich, Tempkin, Halsey, Harkins-Jura and Dubinin-Radushkevich models were applied to determine the characteristic parameters of the adsorption process. Isotherm studies showed that the Langmuir isotherm for MWCNT-Chi and Freundlich and Halsey models for both adsorbents were found to best represent the measured sorption data. In addition, the results of Dubinin-Radushkevich model confirmed the physical adsorption. Negative ΔG° values for MWCNT-Chi and positive ones for MWCNT-COOH indicated the nature of spontaneous and unspontaneous, respectively for adsorption process in the range of the studied concentrations. In addition, picric acid molecules can be desorbed from MWCNT-Chi up to 90% at pH = 9 and that the consumed MWCNT-Chi could be reutilized up to 5th cycle of regeneration. Copyright © 2017 Elsevier B.V. All rights reserved.

Heavy Metal Soil Contamination at U.S. Army Installations: Proposed Research and Strategy for Technology Development

DTIC Science & Technology

1994-03-01

substrates that form the basis of the soil, such as carbonates, clay minerals, organic matter, iron and manganese oxides and hydroxides, sulfides, or...32 10 25 2.5 32 to 64 7 20 1.4 Total 100 200.7 interstitial water, clay minerals, sulfides, carbonates, organic matter, hydrous iron and manganese ...condensation reaction with OH- groups on the surface of (silicon, iron, manganese , and aluminum) com- pounds (Calmano and Forsmer 1983). Sorption-based

Purification of metal finishing waste waters with zeolites and activated carbons.

PubMed

Leinonen, H; Lehto, J

2001-02-01

Sixteen zeolites and 5 activated carbons were tested for the removal of nickel, zinc, cadmium, copper, chromium, and cobalt from waste simulants mimicking effluents produced in metal plating plants. The best performances were obtained from 4 zeolites: A, X, L, and ferrierite types and from 2 carbon types made from lignite and peat. The distribution coefficients for these sorbents were in the range of 10,000-440,000 ml/g. Column experiments showed that the most effective zeolites for Zn, Ni, Cu, and Cd were A and X type zeolites. The activated carbons, Hydrodarco 3000 and Norit Row Supra, exhibited good sorption properties for metals in aqueous solutions containing complexing agents.

Evaluation of estimation methods for organic carbon normalized sorption coefficients

USGS Publications Warehouse

Baker, James R.; Mihelcic, James R.; Luehrs, Dean C.; Hickey, James P.

1997-01-01

A critically evaluated set of 94 soil water partition coefficients normalized to soil organic carbon content (Koc) is presented for 11 classes of organic chemicals. This data set is used to develop and evaluate Koc estimation methods using three different descriptors. The three types of descriptors used in predicting Koc were octanol/water partition coefficient (Kow), molecular connectivity (mXt) and linear solvation energy relationships (LSERs). The best results were obtained estimating Koc from Kow, though a slight improvement in the correlation coefficient was obtained by using a two-parameter regression with Kow and the third order difference term from mXt. Molecular connectivity correlations seemed to be best suited for use with specific chemical classes. The LSER provided a better fit than mXt but not as good as the correlation with Koc. The correlation to predict Koc from Kow was developed for 72 chemicals; log Koc = 0.903* log Kow + 0.094. This correlation accounts for 91% of the variability in the data for chemicals with log Kow ranging from 1.7 to 7.0. The expression to determine the 95% confidence interval on the estimated Koc is provided along with an example for two chemicals of different hydrophobicity showing the confidence interval of the retardation factor determined from the estimated Koc. The data showed that Koc is not likely to be applicable for chemicals with log Kow < 1.7. Finally, the Koc correlation developed using Kow as a descriptor was compared with three nonclass-specific correlations and two 'commonly used' class-specific correlations to determine which method(s) are most suitable.

Impacts of heterogeneous organic matter on phenanthrene sorption--Different soil and sediment samples

USGS Publications Warehouse

Karapanagioti, Hrissi K.; Childs, Jeffrey; Sabatini, David A.

2001-01-01

Organic petrography has been proposed as a tool for characterizing the heterogeneous organic matter present in soil and sediment samples. A new simplified method is proposed as a quantitative means of interpreting observed sorption behavior for phenanthrene and different soils and sediments based on their organic petrographical characterization. This method is tested under singe solute conditions and at phenanthrene concentration of 1 μg/L. Since the opaque organic matter fraction dominates the sorption process, we propose that by quantifying this fraction one can interpret organic content normalized sorption distribution coefficient (Koc) values for a sample. While this method was developed and tested for various samples within the same aquifer, in the current study the method is validated for soil and sediment samples from different sites that cover a wide range of organic matter origin, age, and organic content. All 10 soil and sediment samples studied had log Koc values for the opaque particles between 5.6 and 6.8. This range of Koc values illustrates the heterogeneity of opaque particles between sites and geological formations and thus the need to characterize the opaque fraction of materials on a site-by-site basis.

Long residence times of rapidly decomposable soil organic matter: application of a multi-phase, multi-component, and vertically-resolved model (TOUGHREACTv1) to soil carbon dynamics

NASA Astrophysics Data System (ADS)

Riley, W. J.; Maggi, F. M.; Kleber, M.; Torn, M. S.; Tang, J. Y.; Dwivedi, D.; Guerry, N.

2014-01-01

Accurate representation of soil organic matter (SOM) dynamics in Earth System Models is critical for future climate prediction, yet large uncertainties exist regarding how, and to what extent, the suite of proposed relevant mechanisms should be included. To investigate how various mechanisms interact to influence SOM storage and dynamics, we developed a SOM reaction network integrated in a one-dimensional, multi-phase, and multi-component reactive transport solver. The model includes representations of bacterial and fungal activity, multiple archetypal polymeric and monomeric carbon substrate groups, aqueous chemistry, aqueous advection and diffusion, gaseous diffusion, and adsorption (and protection) and desorption from the soil mineral phase. The model predictions reasonably matched observed depth-resolved SOM and dissolved organic carbon (DOC) stocks in grassland ecosystems as well as lignin content and fungi to aerobic bacteria ratios. We performed a suite of sensitivity analyses under equilibrium and dynamic conditions to examine the role of dynamic sorption, microbial assimilation rates, and carbon inputs. To our knowledge, observations do not exist to fully test such a complicated model structure or to test the hypotheses used to explain observations of substantial storage of very old SOM below the rooting depth. Nevertheless, we demonstrated that a reasonable combination of sorption parameters, microbial biomass and necromass dynamics, and advective transport can match observations without resorting to an arbitrary depth-dependent decline in SOM turnover rates, as is often done. We conclude that, contrary to assertions derived from existing turnover time based model formulations, observed carbon content and δ14C vertical profiles are consistent with a representation of SOM dynamics consisting of (1) carbon compounds without designated intrinsic turnover times, (2) vertical aqueous transport, and (3) dynamic protection on mineral surfaces.

Fate and Distribution of Heavy Metals in Wastewater Irrigated Calcareous Soils

PubMed Central

Stietiya, Mohammed Hashem; Duqqah, Mohammad; Udeigwe, Theophilus; Zubi, Ruba; Ammari, Tarek

2014-01-01

Accumulation of heavy metals in Jordanian soils irrigated with treated wastewater threatens agricultural sustainability. This study was carried out to investigate the environmental fate of Zn, Ni, and Cd in calcareous soils irrigated with treated wastewater and to elucidate the impact of hydrous ferric oxide (HFO) amendment on metal redistribution among soil fractions. Results showed that sorption capacity for Zarqa River (ZR1) soil was higher than Wadi Dhuleil (WD1) soil for all metals. The order of sorption affinity for WD1 was in the decreasing order of Ni > Zn > Cd, consistent with electrostatic attraction and indication of weak association with soil constituents. Following metal addition, Zn and Ni were distributed among the carbonate and Fe/Mn oxide fractions, while Cd was distributed among the exchangeable and carbonate fractions in both soils. Amending soils with 3% HFO did not increase the concentration of metals associated with the Fe/Mn oxide fraction or impact metal redistribution. The study suggests that carbonates control the mobility and bioavailability of Zn, Ni, and Cd in these calcareous soils, even in presence of a strong adsorbent such as HFO. Thus, it can be inferred that in situ heavy metal remediation of these highly calcareous soils using iron oxide compounds could be ineffective. PMID:24723833

Facile low-temperature one-step synthesis of pomelo peel biochar under air atmosphere and its adsorption behaviors for Ag(I) and Pb(II).

PubMed

Zhao, Tuo; Yao, Ying; Li, Danrong; Wu, Feng; Zhang, Cunzhong; Gao, Bin

2018-05-29

This study prepared a novel low-cost surface functionalized carbon adsorbent (PPC) from biomass waste (pomelo peel) through a facile low-temperature (250 °C) one-step method under regular air atmosphere. The adsorption performance and mechanism of the carbon material for Ag(I) and Pb(II) were investigated by a range of sorption experiments and characterizations including SEM, EDX, XRD and FTIR. Sorption experimental results suggested that PPC had high adsorption capacities of 137.4 and 88.7 mg/g for Ag(I) and Pb(II), respectively, with adsorbent dosage of 2 g/L at unadjusted solution pH and room temperature (23 ± 1 °C). The characterization results indicated high-efficiency removal of the heavy metals by PPC was attributed to the strong chemical adsorption involving that Ag(I) ions were reduced as metallic Ag particles by oxygenic functional groups and Pb(II) ions were precipitated as Pb 5 (PO 4 ) 3 OH crystals by phosphorous functional groups on the carbon surfaces. This study provides the possibility of synthesis high-efficient adsorbent using economic and environmental-friendly approach with low energy consumption. Copyright © 2018 Elsevier B.V. All rights reserved.

Wicking Tests for Unidirectional Fabrics: Measurements of Capillary Parameters to Evaluate Capillary Pressure in Liquid Composite Molding Processes.

PubMed

Pucci, Monica Francesca; Liotier, Pierre-Jacques; Drapier, Sylvain

2017-01-27

During impregnation of a fibrous reinforcement in liquid composite molding (LCM) processes, capillary effects have to be understood in order to identify their influence on void formation in composite parts. Wicking in a fibrous medium described by the Washburn equation was considered equivalent to a flow under the effect of capillary pressure according to the Darcy law. Experimental tests for the characterization of wicking were conducted with both carbon and flax fiber reinforcement. Quasi-unidirectional fabrics were then tested by means of a tensiometer to determine the morphological and wetting parameters along the fiber direction. The procedure was shown to be promising when the morphology of the fabric is unchanged during capillary wicking. In the case of carbon fabrics, the capillary pressure can be calculated. Flax fibers are sensitive to moisture sorption and swell in water. This phenomenon has to be taken into account to assess the wetting parameters. In order to make fibers less sensitive to water sorption, a thermal treatment was carried out on flax reinforcements. This treatment enhances fiber morphological stability and prevents swelling in water. It was shown that treated fabrics have a linear wicking trend similar to those found in carbon fabrics, allowing for the determination of capillary pressure.

Impact of carbon, oxygen and sulfur content of microscale zerovalent iron particles on its reactivity towards chlorinated aliphatic hydrocarbons.

PubMed

Velimirovic, Milica; Larsson, Per-Olof; Simons, Queenie; Bastiaens, Leen

2013-11-01

Zerovalent iron (ZVI) abiotically degrades several chlorinated aliphatic hydrocarbons (CAHs) via reductive dechlorination, which offers perspectives for in situ groundwater remediation applications. The difference in reactivity between ZVI particles is often linked with their specific surface area. However, other parameters may influence the reactivity as well. Earlier, we reported for a set of microscale zerovalent iron (mZVI) particles the disappearance kinetic of different CAHs which were collected under consistent experimental conditions. In the present study, these kinetic data were correlated with the carbon, oxygen and sulfur content of mZVI particles. It was confirmed that not only the specific surface area affects the disappearance kinetic of CAHs, but also the chemical composition of the mZVI particles. The chemical composition, in addition, influences CAHs removal mechanism inducing sorption onto mZVI particles instead of dechlorination. Generally, high disappearance kinetic of CAHs was observed for particles containing less oxygen. A high carbon content, on the other hand, induced nonreactive sorption of the contaminants on the mZVI particles. To obtain efficient remediation of CAHs by mZVI particles, this study suggested that the carbon and oxygen content should not exceed 0.5% and 1% respectively. Finally, the efficiency of the mZVI particles may be improved to some extent by enriching them with sulfur. However, the impact of sulfur content on the reactivity of mZVI particles is less pronounced than that of the carbon and oxygen content. Copyright © 2013 Elsevier Ltd. All rights reserved.

Differential Millennial-scale Responses of Terrestrial Carbon Cycling Dynamics to Warming from two Contrasting Lake Catchments in Arctic Alaska

NASA Astrophysics Data System (ADS)

Longo, W. M.; Huang, Y.; Russell, J. M.; Giblin, A. E.; McNichol, A. P.; Xu, L.; Daniels, W.

2016-12-01

Earth's permafrost carbon (C) reservoir is more than twice as large as global atmospheric C and its vulnerability to warming makes it a significant potential feedback to climate change. Predicted rates of warming could result in the release of 5 to 15% of permafrost C to the atmosphere by 2100 (Schuur et al., 2015); however the uncertainty around this estimate hinders our ability to quantify the arctic temperature-carbon feedback. To elucidate the long-term response of terrestrial C to warming in regions underlain by continuous permafrost, we present geologic records of changes in temperature and terrestrial C cycling dynamics from sediment cores from two contrasting lake catchments in arctic Alaska. The sediment records feature independent chronologies, biomarker-based temperature reconstructions, and geochemical measurements of vascular plant biomarkers (lignin phenols) that provide insight into terrestrial carbon quality, its release from permafrost soils and its transit time on the landscape. Our results indicate that both abrupt and sustained increases in temperature over the past 20,000 years resulted in increased carbon normalized yields of lignin phenols (Λ8, Λ6), which indicate increased mobilization of terrestrial organic carbon from permafrost soils. Lignin phenol indicators of terrestrial carbon quality (Ad:Al(s), Ad:Al(v)), indicated that carbon quality decreased with increasing temperature. These results demonstrate covariation between temperature and both the decay of terrestrial organic matter and lignin alteration resulting from dissolution and sorption processes. Compound specific radiocarbon analyses of lignin phenols and their offsets from depositional ages quantify transit times of terrestrial carbon on the landscape. These measurements revealed the presence of a persistent "pre-aged" terrestrial organic carbon pool, which is likely sourced from degrading permafrost. We also observe different responses of terrestrial organic carbon cycling to temperature that depend on landscape characteristics. C cycling responses are pronounced in the low-relief, Pleistocene-aged catchment of lake E5, and more muted in Lake Fog 2, which exists in a higher-relief and younger catchment. Mechanisms differentiating the responses of these catchments are discussed.

One decade of research into the fate and transport of carbon-based nanomaterials - Lessons learnt and future perspectives

NASA Astrophysics Data System (ADS)

Hüffer, Thorsten; Hofmann, Thilo

2016-04-01

Carbon-based nanomaterials (CNM) exhibit unique physico-chemical properties (e.g., large surface area to volume ratios, electron delocalization), which make them promising for a great number of applications. The production, use, and disposal of CNM and CNM-containing products will inevitably result in the release of these materials into the environment. The fate and transport of CNM greatly depends on their physico-chemical properties and surrounding environmental conditions. This field of research has constantly increased over recent years. Yet little is known on how transformation processes such as changes in surface properties or aggregation influence their interaction with other environmental species (i.e., solid surfaces or contaminants). For example, changes in redox chemistry in combination with irradiation have shown to significantly alter the surface chemistry of C60 fullerenes and consequently decreased their sorption affinity towards non-polar organic contaminants [1]. The presence of natural organic matter (NOM) seems to play a major role on the aggregation of CNM; however, the results are not consistent whether this leads to an increase or decrease in interactions with solid surfaces or contaminants. Either increased interactions resulting from a higher dispersion of CNM or decreased interactions of CNM, which was assigned to an offset of "creating" new sorption sites due to increased dispersion by a reduced accessibility of polar moieties. For the latter effect, NOM was proposed to either directly compete for sorption sites on CNM surface or a blocking of CNM pores by large NOM molecules [2]. The potential consequences of these changes in surface properties of CNM on their toxic effects on microorganisms have only been partially examined. For an environmental risk assessment, data on the occurrence of CNM is obligatory but to date the environmental concentrations of CNM are still difficult to assess due to still unsolved analytical issues in matrix separation and the discrimination of CNM from naturally present particles with similar dimensions and properties (e.g., soot or colloids). Recently, progress has been made to characterize the aggregation and to determine the occurrence of (functionalized) fullerenes using asymmetrical flow field-flow fractionation coupled to a LC-HR-MS [3]. In this contribution, the major results during the last decade of environmental research into CNM will be reviewed with the focus on their analyses and characterization, and interactions with solid surfaces. References: [1] Hüffer, T., Kah, M., Hofmann, T., Schmidt, T.C. (2013) How Redox Conditions and Irradiation Affect Sorption of PAHs by Dispersed Fullerenes (nC60). Environmental Science & Technology, 47(13), 6935-6942. [2] Hüffer, T., Schroth, S., Schmidt, T.C. (2015) Influence of humic acids on sorption of alkanes by carbon nanotubes - Implications for the dominant sorption mode. Chemosphere, 119, 1169-1175. [3] Kolkman, A., Emke, E., Bauerlein, P.S., Carboni, A., Tran, D.T., terLaak, T.L., vanWezel, A.P., deVoogt, P. (2013) Analysis of (Functionalized) Fullerenes in Water Samples by Liquid Chromatography Coupled to High-Resolution Mass Spectrometry. Analytical Chemistry, 85(12), 5867-5874.

Sorption of Perfluorochemicals to Matrices Relevant to Sites Impacted by Aqueous Film-Forming Foam

NASA Astrophysics Data System (ADS)

Sepulvado, J.; Higgins, C.

2011-12-01

Perfluorochemicals are a class of emerging contaminants consisting of fluorinated surfactants that are chemically and thermally stable and which contain a fluorocarbon tail that is both hydro- and oleophobic. Because of these unique properties, PFCs have a wide variety of uses including food paper packaging products, stain repellants, nonstick coatings, and aqueous film-forming foams (AFFF). At fire-training facilities, repeated application of AFFF is used to extinguish hydrocarbon fuel fires ignited for training purposes. The presence of perfluochemicals (PFCs) in groundwater as a result of repeated AFFF application at these facilities has been documented. Due to factors such as the recent push towards regulation of PFCs in drinking water, concerns have arisen about the fate of these compounds in the subsurface. Groundwater plumes containing PFC subclasses such as perfluorocarboxylic acids (PFCAs), perfluoroalkylsulfonates (PFAS), and fluorotelomer sulfonates (FtSs) in the μg/L to mg/L range have been detected. These plumes also may contain co-contaminants such as hydrocarbon fuel components and chlorinated solvents, some of which may exist as nonaqueous phase liquids (NAPL). This study examined the sorption of PFCs to soil and aquifer material across the concentration range applicable to AFFF-impacted sites (μg/L - mg/L) and looked at the impact of co-contaminants, including NAPL, on PFC sorption. PFC sorption was variable and indicated that similar to previous work on PFC sorption to sediment, subsurface PFC transport will depend on factors such as the sorbent organic carbon content, PFC subclass, solution chemistry, and PFC chain length.

Sorption of arsenic to biogenic iron (oxyhydr)oxides produced in circumneutral environments

NASA Astrophysics Data System (ADS)

Sowers, Tyler D.; Harrington, James M.; Polizzotto, Matthew L.; Duckworth, Owen W.

2017-02-01

Arsenic (As) is a widespread and problematic pollutant that can be derived from natural or anthropogenic sources. Iron (oxyhydr)oxides readily sorb As and thus play critical roles in As cycling in terrestrial environments; however, little is known about the affinity and mechanism of As sorption by biogenic iron (oxyhydr)oxides formed in circumneutral environments. To investigate this, we conducted sorption isotherm and kinetics experiments to compare As(V) and As(III) sorption to synthetic 2-line ferrihydrite and iron biominerals harvested from the hyporheic zone of an uncontaminated creek. Inductively coupled plasma mass spectrometry (ICP-MS) was used to quantify both As(V) and As(III), and X-ray absorption spectroscopy (XAS) was utilized to obtain As and Fe K-edge spectra for As(V) and As(III) sorbed to environmentally collected and laboratory produced Fe(III) minerals. All environmental Fe(III) biominerals were determined to be structurally similar to 2-line ferrihydrite. However, environmental Fe(III) biominerals have a surface area normalized affinity for As(V) and for As(III) that is greater than or equivalent to synthetic 2-line ferrihydrite. Whereas the extent of sorption was similar for As(III) on all minerals, As(V) sorption to environmental Fe(III) biominerals was approximately three times higher than what was observed for synthetic 2-line ferrihydrite. Structural modeling of EXAFS spectra revealed that the same surface complexation structure was formed by As(V) and by As(III) on environmental Fe(III) biominerals and ferrihydrite. These results suggest that, despite similarities in binding mechanisms, Fe(III) biominerals may be more reactive sorbents that synthetic surrogates often used to model environmental reactivity.

Factors influencing inapplicability of cosolvency-induced model on organic acid sorption onto humic substance from methanol mixture.

PubMed

Kim, Minhee; Kim, Juhee; Kim, Jeong-Gyu; Hyun, Seunghun

2015-10-01

Applicability of cosolvency model for describing the sorption of organic acids to humic substance was investigated by analyzing dataset of sorption (K m) and solubility (S m) of selected solutes (benzoic acid, 1-naphthoic acid, 2,4-dichlorophenoxyacetic acid, and 2,4,6-trichlorophenol (2,4,6-TCP)) as a function of pH(appCME) (apparent pH of liquid phase) and f c (methanol volume fractions). For all solutes, the K m decreased with f c with the K m reduction being less than the S m-based prediction. The slope of log K m-f c plot in the three organic carboxylic acids was well correlated with their cosolvency power, whereas the data of organic phenolic acid (2,4,6-TCP) was placed above the trend, indicating the different actions of functional groups. The occurrence of Ca(2+) bridge between carboxylate and negatively charged humic surface may explain this phenomenon. Normalizing the K m to the corresponding S m (α' = K m/S m) was not in unity over the pH(app)-f c range but decreased with f c, indicating a possible structural modification of sorption domain favoring extra sorption. For a given solute, the α' of neutral species was always greater than that of anionic species, showing that extra interaction will be likely at pH(app)

LOW CONCENTRATION MERCURY SORPTION MECHANISMS AND CONTROL BY CALCIUM-BASED SORBENTS; APPLICATION IN COAL-FIRED PROCESSES

EPA Science Inventory

The capture of elemental mercury (Hgo) and mercuric chloride (HgCl2) by three types of calcium (Ca)-based sorbents was examined in this bench-scale study under conditions prevalent in coal fired utilities. Ca-based sorbent performances were compared to that of an activated carbon...

SORPTION OF MERCURY SPECIES BY ACTIVATED CARBONS AND CALCIUM-BASES SORBENTS: EFFECT OF TEMPERATURE, MERCURY CONCENTRATION AND ACID GASES

EPA Science Inventory

Bench-scale studies of mercury/sorbent reactions were conducted to understand mechanistic limitations of field-scale attempts to reduce emissions of mercury from combustion processes. The effects of temperature (60 - 140 degrees C), sulfur dioxide (SO2, 1000 ppm ), hydrogen chlor...

Removal of antimony (III) and cadmium (II) from aqueous solution using animal manure-derived hydrochars and pyrochars

USDA-ARS?s Scientific Manuscript database

Very few studies have been done to explore the impact of hydrothermal carbonization and conventional dry pyrolysis in the sorption capacities of biochars towards heavy metals. In this study, hydrochars and pyrochars prepared from swine solids and poultry litter were characterized and were used as ad...

Biological and physicochemical properties of carbon-graphite fibre-reinforced polymers intended for implant suprastructures.

PubMed

Segerström, Susanna; Sandborgh-Englund, Gunilla; Ruyter, Eystein I

2011-06-01

The aim of this study was to determine water sorption, water solubility, dimensional change caused by water storage, residual monomers, and possible cytotoxic effects of heat-polymerized carbon-graphite fibre-reinforced composites with different fibre loadings based on methyl methacrylate/poly(methyl methacrylate) (MMA/PMMA) and the copolymer poly (vinyl chloride-co-vinyl acetate). Two different resin systems were used. Resin A contained ethylene glycol dimethacrylate (EGDMA) and 1,4-butanediol dimethacrylate (1,4-BDMA); the cross-linker in Resin B was diethylene glycol dimethacrylate (DEGDMA). The resin mixtures were reinforced with 24, 36 and 47 wt% surface-treated carbon-graphite fibres. In addition, polymer B was reinforced with 58 wt% fibres. Water sorption was equal to or below 3.34±1.18 wt%, except for the 58 wt% fibre loading of polymer B (5.27±1.22 wt%). Water solubility was below 0.36±0.015 wt%, except for polymer B with 47 and 58 wt% fibres. For all composites, the volumetric increase was below 0.01±0.005 vol%. Residual MMA monomer was equal to or below 0.68±0.05 wt% for the fibre composites. The filter diffusion test and the (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) (MTT) assay demonstrated no cytotoxicity for the carbon-graphite fibre-reinforced composites, and residual cross-linking agents and vinyl chloride were not detectable by high-performance liquid chromatography (HPLC) analysis. © 2011 Eur J Oral Sci.

Demonstration of Critical Systems for Propellant Production on Mars for Science and Exploration Missions

NASA Technical Reports Server (NTRS)

Linne, Diane L.; Gaier, James R.; Zoeckler, Joseph G.; Kolacz, John S.; Wegeng, Robert S.; Rassat, Scot D.; Clark, D. Larry

2013-01-01

A Mars hopper has been proposed as a Mars mobility concept that will also demonstrate and advance in-situ resource utilization. The components needed in a Mars propellant production plant have been developed to various levels of technology maturity, but there is little experience with the systems in a Mars environment. Two systems for the acquisition and compression of the thin carbon dioxide atmosphere were designed, assembled, and tested in a Mars environment chamber. A microchannel sorption pump system was able to raise the pressure from 7 Torr to 450 Torr or from 12 Torr to over 700 Torr in two stages. This data now provides information needed to make additional improvements in the sorption pump technology to increase performance, although a system-level analysis might prove that some amount of pre- or post-compression may be a preferred solution. A mini cryofreezer system was also evaluated as an alternative method for carbon dioxide acquisition and compression. Finally, an electrolysis system was tested and successfully demonstrated start-up operation and thermal stability of all components during long-term operation in the chamber.

Distribution of pyrethroid insecticides in secondary wastewater effluent

PubMed Central

Parry, Emily; Young, Thomas M.

2014-01-01

Although the freely dissolved form of hydrophobic organic chemicals may best predict aquatic toxicity, differentiating between dissolved and particle bound forms is challenging at environmentally relevant concentrations for compounds with low toxicity thresholds such as pyrethroid insecticides. We investigated the distribution of pyrethroids among three forms: freely dissolved, complexed with dissolved organic carbon (DOC), and sorbed to suspended particulate matter, during a yearlong study at a secondary wastewater treatment plant. Effluent was fractionated by laboratory centrifugation to determine if sorption was driven by particle size. Linear distribution coefficients were estimated for pyrethroid sorption to suspended particulate matter (Kid) and dissolved organic carbon (Kidoc) at environmentally relevant pyrethroid concentrations. Resulting Kid values were higher than those reported for other environmental solids, and variation between sampling events correlated well with available particle surface area. Fractionation results suggest that no more than 40% of the pyrethroid remaining in secondary effluent could be removed by extending settling periods. Less than 6%of the total pyrethroid load in wastewater effluent was present in the dissolved form across all sampling events and chemicals. PMID:23939863

DOE Office of Scientific and Technical Information (OSTI.GOV)

Uchrin, C.G.; Mangels, G.

Studies examining sorption equilibria of benzene and toluene to New Jersey coastal plain aquifer solids were performed. Adsorption to the Cohansey aquifer solids, a coarse to fine grade sand with a 2.6% organic carbon content, and to the Potomac-Raritan-Magothy aquifer solids, a sandy loam with a 1.3% organic carbon content, was found to be dependent on adsorber mass. Equilibrium adsorption could be characterized by either linear or Freundlich isotherms. Toluene exhibited a greater affinity to sorb than benzene. Greater adsorption was in general observed for both substances to the Cohansey material, which was attributed to its greater organic matter (carbon)more » content. Consecutive desorption experiments displayed an apparent hysteresis.« less

Sorption studies of nickel ions onto activated carbon

NASA Astrophysics Data System (ADS)

Joshi, Parth; Vyas, Meet; Patel, Chirag

2018-05-01

Activated porous carbons are made through pyrolysis and activation of carbonaceous natural as well as synthetic precursors. The use of low-cost activated carbon derived from azadirachta indica, an agricultural waste material, has been investigated as a replacement for the current expensive methods of removing nickel ions from wastewater. The temperature variation study showed that the nickel ions adsorption is endothermic and spontaneous with increased randomness at the solid solution interface. Significant effect on adsorption was observed on varying the pH of the nickel ion solutions. Therefore, this study revealed that azadirachta indica can serve as a good source of activated carbon with multiple and simultaneous metal ions removing potentials and may serve as a better replacement for commercial activated carbons in applications that warrant their use.

Effect of Mechanical Impact Energy on the Sorption and Diffusion of Moisture in Reinforced Polymer Composite Samples on Variation of Their Sizes

NASA Astrophysics Data System (ADS)

Startsev, V. O.; Il'ichev, A. V.

2018-05-01

The effect of mechanical impact energy on the sorption and diffusion of moisture in polymer composite samples on variation of their sizes was investigated. Square samples, with sides of 40, 60, 80, and 100 mm, made of a KMKU-2m-120.E0,1 carbon-fiber and KMKS-2m.120.T10 glass-fiber plastics with different resistances to calibrated impacts, were compared. Impact loading diagrams of the samples in relation to their sizes and impact energy were analyzed. It is shown that the moisture saturation and moisture diffusion coefficient of the impact-damaged materials can be modeled by Fick's second law with account of impact energy and sample sizes.

Adsorption of chromium ions from aqueous solution by using activated carbo-aluminosilicate material from oil shale.

PubMed

Shawabkeh, Reyad Awwad

2006-07-15

A novel activated carbo-aluminosilicate material was prepared from oil shale by chemical activation. The chemicals used in the activation process were 95 wt% sulfuric and 5 wt% nitric acids. The produced material combines the sorption properties and the mechanical strength of both activated carbon and zeolite. An X-ray diffraction analysis shows the formation of zeolite Y, Na-X, and A-types, sodalite, sodium silicate, mullite, and cancrinite. FT-IR spectrum shows the presence of carboxylic, phenolic, and lactonic groups on the surface of this material. The zero point of charge estimated at different mass to solution ratio ranged from 7.9 to 8.3. Chromium removal by this material showed sorption capacity of 92 mg/g.

Intense Electrochemical Oxidation on Graphitized Carbon Electrodes in the Presence of Ozone

NASA Astrophysics Data System (ADS)

Klochikhin, V. L.; Potapova, G. F.; Putilov, A. V.

2018-06-01

A new intense oxidation process for water treatment in which oxidation with ozone is coupled to electrochemical processes is described, and the results from its application to water purification are presented along with the discussion of its practical implementation. The use of graphitized carbon materials for this process is explained and tested experimentally. The use of glassy carbon for the anode enables us to achieve very high (up to 25 vol %) concentrations of ozone in the generated ozone-oxygen mixture. The material used for the cathode—graphitized carbon cloth (GCC) reinforced with Ni allows different electrocatalytic processes to proceed on its developed surface, and combines the high sorption capacity of this cathode and potentialcontrolled selectivity of cathodic electrochemical processes.

Carbon dioxide and methane sorption in high volatile bituminous coals from Indiana, USA

USGS Publications Warehouse

Mastalerz, Maria; Gluskoter, Harold J.; Rupp, J.

2004-01-01

Samples of coals from several coalbeds in Indiana were analyzed for CO2 and CH4 sorption capacity using a high-pressure adsorption isotherm technique. Coal quality and petrographic composition of the coals were determined to study their relationships to the volume of CO2 and CH4 that could be sorbed into the coal. At the temperature of 17 ??C and 400 psi (??? 2.8 MPa), the coals can sorb (on dry ash-free basis) from 4 to 6.3 m3/ton (128-202 scf/ton) of CH4 and 19.5-24.6 m3/ton4 (624 to 788 scf/ton) of CO2. The ratio of CO2/CH4 at these conditions ranges from 3.5 to 5.3 and decreases with an increasing pressure for all coals. The coals studied are of a very similar coal rank (Ro from 0.48 to 0.62%) but of varying petrographic composition, and CO2 sorption volumes appear to be positively correlated to the content of maceral telocollinite. ?? 2004 Elsevier B.V. All rights reserved.

Sorption of paracetamol onto biomaterials.

PubMed

Ferchichi, Maroua; Dhaouadi, Hatem

2016-01-01

Pharmaceutical residues released into the environment are posing more and more public health problems. It is worthwhile to study the retention of pharmaceuticals residues by adsorption on solid supports. Batch sorption experiments are intended to identify the adsorption isotherms of the pharmaceutically active ingredient on the biomaterials. The results obtained in this study have shown that the retention possibilities of these compounds by bio-adsorbents (clay and sand) are not significant. The negligible sorption for these media is explained by the low hydrophobicity of paracetamol (Log K(ow) = 0.46). The retention of paracetamol on the dehydrated sewage sludge and on Posidonia oceanica showed a relatively significant adsorption with a maximal quantity of 0.956 mg g(-1) and 1.638 mg g(-1) for the dehydrate sludge and P. oceanica, respectively. On the other hand, the study of paracetamol retention on the powdered activated carbon showed a high adsorption capacity of about 515.27 mg g(-1). Isotherm data show a good fit with Langmuir's model. An infrared analysis is carried out. It shows identical bands before and after adsorption, with some modifications.

Removal of lead from aqueous solutions with a treated spent bleaching earth.

PubMed

Mana, Mohamed; Ouali, Mohand Said; Lindheimer, Marc; Menorval, Louis Charles de

2008-11-30

A spent bleaching earth from an edible oil refinery has been treated by impregnation with a normal sodium hydroxide solution followed by mild thermal treatment (100 degrees C). The obtained material (TSBE) was washed, dried and characterized by X-ray diffraction, FTIR, SEM, BET and thermal analysis. The clay structure was not apparently affected by the treatment and the impregnated organic matter was quantitatively removed. We have investigated the sorption of lead on this material, the spent bleaching earth (SBE) and the virgin bleaching earth (VBE). The kinetic results fit the pseudo second-order kinetic model and the Weber & Morris, intraparticle diffusion model. The pH had effect on the sorption efficiency. The sorption isotherms followed the Langmuir model for various sorbent concentrations with good values of determination coefficient. A comparison between the results obtained with this material and those of the literature highlighted a good removal capacity of the treated spent bleaching earth at low cost.

Sorption of Hydrophobic Organic Compounds on Natural Sorbents and Organoclays from Aqueous and Non-Aqueous Solutions: A Mini-Review

PubMed Central

Moyo, Francis; Tandlich, Roman; Wilhelmi, Brendan S.; Balaz, Stefan

2014-01-01

Renewed focus on the sorption of hydrophobic organic chemicals (HOCs) onto mineral surfaces and soil components is required due to the increased and wider range of organic pollutants being released into the environment. This mini-review examines the possibility of the contribution and mechanism of HOC sorption onto clay mineral sorbents such as kaolinite, and soil organic matter and the possible role of both in the prevention of environmental contamination by HOCs. Literature data indicates that certain siloxane surfaces can be hydrophobic. Therefore soils can retain HOCs even at low soil organic levels and the extent will depend on the structure of the pollutant and the type and concentration of clay minerals in the sorbent. Clay minerals are wettable by nonpolar solvents and so sorption of HOCs onto them from aqueous and non-aqueous solutions is possible. This is important for two reasons: firstly, the movement and remediation of soil environments will be a function of the concentration and type of clay minerals in the soil. Secondly, low-cost sorbents such as kaolinite and expandable clays can be added to soils or contaminated environments as temporary retention barriers for HOCs. Inorganic cations sorbed onto the kaolinite have a strong influence on the rate and extent of sorption of hydrophobic organic pollutants onto kaolinite. Structural sorbate classes that can be retained by the kaolinite matrix are limited by hydrogen bonding between hydroxyl groups of the octahedral alumosilicate sheet and the tetrahedral sheet with silicon. Soil organic carbon plays a key role in the sorption of HOCs onto soils, but the extent will be strongly affected by the structure of the organic soil matter and the presence of soot. Structural characterisation of soil organic matter in a particular soil should be conducted during a particular contamination event. Contamination by mining extractants and antibiotics will require renewed focus on the use of the QSAR approaches in the context of the sorption of HOCs onto clay minerals from aqueous and non-aqueous solutions. PMID:24821385

Interfacial Interaction of Titania Nanoparticles and Ligated Uranyl Species: A Relativistic DFT Investigation.

PubMed

Zhao, Hong-Bo; Zheng, Ming; Schreckenbach, Georg; Pan, Qing-Jiang

2017-03-06

To understand interfacial behavior of actinides adsorbed onto mineral surfaces and unravel their structure-property relationship, the structures, electronic properties, and energetics of various ligated uranyl species adsorbed onto TiO 2 surface nanoparticle clusters (SNCs) were examined using relativistic density functional theory. Rutile (110) and anatase (101) titania surfaces, experimentally known to be stable, were fully optimized. For the former, models studied include clean and water-free Ti 27 O 64 H 20 (dry), partially hydrated (Ti 27 O 64 H 20 )(H 2 O) 8 (sol) and proton-saturated [(Ti 27 O 64 H 20 )(H 2 O) 8 (H) 2 ] 2+ (sat), while defect-free and defected anatase SNCs involving more than 38 TiO 2 units were considered. The aquouranyl sorption onto rutile SNCs is energetically preferred, with interaction energies of -8.54, -10.36, and -2.39 eV, respectively. Energy decomposition demonstrates that the sorption is dominated by orbital attractive interactions and modified by steric effects. Greater hydrogen-bonding involvement leads to increased orbital interactions (i.e., more negative energy) from dry to sol/sat complexes, while much larger steric interaction in the sat complex significantly reduces the sorption interaction (i.e., more positive energy). For dry SNC, adsorbates were varied from aquo to aquo-carbonato, to carbonato, to hydroxo uranyl species. Longer U-O surf /U-Ti distances and more positive sorption energies were calculated upon introducing carbonato and hydroxo ligands, indicative of weaker uranyl sorption onto the substrate. This is consistent with experimental observations that the uranyl sorption rate decreases upon raising solution pH value or adding carbon dioxide. Anatase SNCs adsorbing aquouranyl are even more exothermic, because more bonds are formed than in the case of rutile. Moreover, the anatase sorption can be tuned by surface defects as well as its Ti and O stoichiometry. All the aquouranyl-SNC complexes show similar character of molecular orbitals and energetic order although differing in highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gaps and orbital energy levels, but changes can be accomplished by adding carbonato and hydroxo ligands.

Toxic substances in surface waters and sediments--A study to assess the effects of arsenic-contaminated alluvial sediment in Whitewood Creek, South Dakota

USGS Publications Warehouse

Kuwabara, James S.; Fuller, Christopher C.

2003-01-01

Field measurements and bioassay experiments were done to investigate the effects of arsenic and phosphorus interactions on sorption of these solutes by the benthic flora (periphyton and submerged macrophytes) in Whitewood Creek, a stream in western South Dakota. Short-term (24-hour) sorption experiments were used to determine arsenic transport characteristics for algae (first-order rate constants for solute sorption, biomass, and accumulation factors) collected in the creek along a transect beginning upstream from a mine discharge point and downgradient through a 57-kilometer reach. Temporal changes in biomass differed significantly between and within sampling sites. Arsenic concentrations in plant tissue increased with distance downstream, but temporal changes in concentrations in tissues differed considerably from site to site. Cultures of Achnanthes minutissima (Bacillariophyceae) and Stichococcus sp. (Chlorophyceae) were isolated from four sites along a longitudinal concentration gradient of dissolved arsenic within the study reach and were maintained at ambient solute concentrations. Arsenic accumulation factors and sorption-rate constants for these isolates were determined as a function of dissolved arsenate and orthophosphate. Cell surfaces of algal isolates exhibited preferential orthophosphate sorption over arsenate. Initial sorption of both arsenate and orthophosphate followed first-order mass transfer for each culturing condition. Although sorption-rate constants increased slightly with increased dissolved-arsenate concentration, algae, isolated from a site with elevated dissolved arsenic in the stream channel, had a significantly slower rate of arsenic sorption compared with the same species isolated from an uncontaminated site upstream. In diel studies, amplitudes of the pH cycles increased with measured biomass except at a site immediately downstream from water-treatment-plant discharge. Inorganic pentavalent arsenic dominated arsenic speciation at all sites?not a surprising result for the well-oxygenated water column along this reach. Concentration fluctuations in dissolved-arsenic species lagged pH fluctuations by approximately 3 hours at the most downstream site, but no discernible lag was observed at an artificially pooled area with an order of magnitude higher biomass. Furthermore, the amplitudes of diel fluctuations in arsenic species were greater at the pooled area than at the most downstream site. Lack of correspondence between changes in dissolved-orthophosphate concentrations and arsenic species may have resulted from preferential sorption of orthophosphate over arsenate by the biomass. Based on carbon-fixation estimates, the phosphorus demand from photosynthetic activity required water-column concentrations to be supplemented by another source such as phosphate regeneration within the benthic community or desorption of particle-bound phosphate.

Acoustic emission and sorptive deformation induced in coals of various rank by the sorption-desorption of gas

NASA Astrophysics Data System (ADS)

Majewska, Zofia; Ziętek, Jerzy

2007-09-01

Simultaneous measurements of acoustic emission (AE) and expansion/contraction of coal samples subjected to gas sorption-desorption processes were conducted on high-and medium-rank coal. The aim of this study was to examine the influence of the coal rank and type of sorbate on measured AE and strain characteristics. The experimental equipment employed in this study consisted of a pressure vessel and associated pressurisation and monitoring units. The arrangement of pressure-vacuum valves permitted the coal sample to be pressurised and depressurised. Carbon-dioxide and methane were used as sorbats. Acoustic emission and strains were recorded continuously for a period of 50 hours during sorption and for at least 12 hours during the desorption process. Tests were conducted on cylindrical coal samples at 298 K. The experimental data were presented as plots of AE basic parameters versus time and in strain diagrams. These studies lead to the following conclusions: 1. There are significant differences in AE and strain characteristics for the two systems (coal-CO2 and coal-CH4); 2. There is a direct influence of rank and type of coal on its behaviour during the sorption-desorption of gas. An attempt has been made to interpret the results obtained on the grounds of the copolymer model of coal structure. More research is needed into this topic in order to get a quantitative description of the observed facts.

Use of carbonised beet pulp carbon for removal of Remazol Turquoise Blue-G 133 from aqueous solution.

PubMed

Dursun, Arzu Y; Tepe, Ozlem; Dursun, Gülbeyi

2013-01-01

Carbonised beet pulp (BPC) produced from agricultural solid waste by-product in sugar industry was used as adsorbent for the removal of Remazol Turquoise Blue-G 133 (RTB-G 133) dye in this study. The kinetics and equilibrium of sorption process were investigated with respect to pH, temperature and initial dye concentration. Adsorption studies with real textile wastewater were also performed. The results showed that adsorption was a strongly pH-dependent process, and optimum pH was determined as 1.0. The maximum dye adsorption capacity was obtained as 47.0 mg g(-1)at the temperature of 25 °C at this pH value. The Freundlich and Langmuir adsorption models were used for describing the adsorption equilibrium data of the dye, and isotherm constants were evaluated depending on sorption temperature. Equilibrium data of RTB-G 133 sorption fitted very well to the Freundlich isotherm. Mass transfer and kinetic models were applied to the experimental data to examine the mechanisms of adsorption and potential rate-controlling steps. It was found that both external mass transfer and intra-particle diffusion played an important role in the adsorption mechanisms of dye and adsorption kinetics followed the pseudo second-order type kinetic model. The thermodynamic analysis indicated that the sorption process was exothermic and spontaneous in nature.

Multi-podant diglycolamides and room temperature ionic liquid impregnated resins: An excellent combination for extraction chromatography of actinides.

PubMed

Gujar, R B; Ansari, S A; Verboom, W; Mohapatra, P K

2016-05-27

Extraction chromatography resins, prepared by impregnating two multi-podant diglycolamide ligands, viz. diglycolamide-functionalized calix[4]arene (C4DGA) and tripodal diglycolamide (T-DGA) dissolved in the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (RTIL: C4mimTf2N) on Chromosorb-W (an inert solid support), gave excellent results for the removal of trivalent actinides from acidic waste solutions. Distribution coefficient measurements on several metal ions showed selective sorption of Am(III) over hexavalent uranyl ions and other fission product elements such as strontium and cesium. The sorbed metal ions could be efficiently desorbed with a complexing solution containing guanidine carbonate and EDTA buffer. The sorption of Am(III) on both resins followed pseudo-second order rate kinetics with rate constants of 1.37×10(-6) and 6.88×10(-7)g/cpmmin for T-DGA and C4DGA resins, respectively. The metal sorption on both resins indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) sorption capacities of 4.83±0.21 and 0.52±0.05mg per g of T-DGA and C4DGA resins, respectively. The results of column studies show that these resins are of interest for a possible application for the recovery of hazardous trivalent actinides from dilute aqueous solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Sorption of Cationic Surfactants to Artificial Cell Membranes: Comparing Phospholipid Bilayers with Monolayer Coatings and Molecular Simulations.

PubMed

Timmer, Niels; Droge, Steven T J

2017-03-07

This study reports the distribution coefficient between phospholipid bilayer membranes and phosphate buffered saline (PBS) medium (D MW,PBS ) for 19 cationic surfactants. The method used a sorbent dilution series with solid supported lipid membranes (SSLMs). The existing SSLM protocol, applying a 96 well plate setup, was adapted to use 1.5 mL glass autosampler vials instead, which facilitated sampling and circumvented several confounding loss processes for some of the cationic surfactants. About 1% of the phospholipids were found to be detached from the SSLM beads, resulting in nonlinear sorption isotherms for compounds with log D MW values above 4. Renewal of the medium resulted in linear sorption isotherms. D MW values determined at pH 5.4 demonstrated that cationic surfactant species account for the observed D MW,PBS . Log D MW,PBS values above 5.5 are only experimentally feasible with lower LC-MS/MS detection limits and/or concentrated extracts of the aqueous samples. Based on the number of carbon atoms, dialkylamines showed a considerably lower sorption affinity than linear alkylamine analogues. These SSLM results closely overlapped with measurements on a chromatographic tool based on immobilized artificial membranes (IAM-HPLC) and with quantum-chemistry based calculations with COSMOmic. The SSLM data suggest that IAM-HPLC underestimates the D MW of ionized primary and secondary alkylamines by 0.8 and 0.5 log units, respectively.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sharma, Prasesh; Mayes, Melanie; Tang, Guoping

Contamination of soils/groundwater by munition compounds (TNT, RDX, HMX) is of significant concern at many U.S. Department of Defense sites. We collected soils from operational ranges in Maryland (APG), Massachusetts (MMR-B and MMR-E) and Washington (JBLM) and conducted sorption/transport studies to investigate effects of soil organic carbon (OC) and clay content on fate of dissolved munition compounds (MCs). Sorption experiments showed higher sorption coefficients [TNT:42-68 kg/L, RDX:6.9-8.7 Kg/L and HMX:2.6-3.1 Kg/L] in OC rich soils (JBLM, MMR-E) compared to clay rich soils MMR-B and APG [TNT:19-21 Kg/L, RDX:2.5-3.4 Kg/L, HMX:0.9-1.2 Kg/L]. In column experiments, breakthrough of MCs was mostly quickermore » in MMR-B and APG soil filled columns compared to MMR-E and JBLM. Between TNT, RDX and HMX, breakthrough was fastest for RDX followed by HMX and TNT for all soil columns. Separation of effluents into dissolved (<3 kDa) vs unfiltered (total) fractions in effluents showed 30-50% of TNT in the fraction >3kDa (colloidal fraction). HMX and RDX were completely associated with dissolved fraction. Results demonstrate that OC rich soils may enhance sorption and delay transport of TNT, RDX and HMX. Furthermore, colloids could contribute to transport of dissolved TNT to a significant amount.« less

Estimation of biotransformation and sorption of emerging organic compounds (EOCs) during artificial recharge through a reactive barrier.

NASA Astrophysics Data System (ADS)

Valhondo, C.; Martinez-Landa, L.; Carrera, J.; Hidalgo, J. J.; Ayora, C.

2016-12-01

The reuse of lesser quality water such as effluents from wastewater treatment plants or effluent-receiving water bodies has been promoted due to the water shortages affecting many regions of the world. Artificial recharge through infiltration basins is known to improve several water quality parameters including the attenuation of emerging organic compounds (EOCs). Many of these contaminants exhibit redox dependent biotransformation because the redox state is one of the factors controlling microbial community development. Together with biotransformation, sorption also affects the behavior of EOCs in their passage through the soil. We studied EOCs attenuation in an infiltration system is located in Sant Vicenç dells Horts on the Llobregat delta (Barcelona, Spain), where the local water agency has an artificial recharge pilot project . The Llobregat river water used for the artificial recharge is affected by treatment plant effluents which contain EOCs. A reactive barrier consisting of vegetable compost, clay, and iron oxide was installed in the bottom of the infiltration basin to enhance biotransformation and sorption of EOCs. The barrier releases dissolved organic carbon, which favors the development of a broad range of redox environments, and supplies neutral, cationic, and anionic surfaces to favor sorption of different types of contaminants. Results were excellent, but quantitative evaluation of the EOCs attenuation requires knowledge of the residence time distribution of infiltrated water. A tracer test was performed by adding tracers to the infiltration water and interpreting the breakthrough curves at diverse monitoring points with a 2D multilayer numerical model. The calibrated model quantify degradation, as a first order law, and sorption through a linear distribution coefficient for ten selected EOCs. Results indicate higher degradation rates and sorption coefficients in the reactive barrier than in the rest of the aquifer for nine and eight of the ten studied EOCs, respectively, which demonstrates the efficiency of the reactive barrier to enhance the removal of EOCs.

Sorption kinetics of TNT and RDX in anaerobic freshwater and marine sediments: Batch studies.

PubMed

Ariyarathna, Thivanka; Vlahos, Penny; Tobias, Craig; Smith, Richard

2016-01-01

Examination of the partitioning of explosives onto sediment in marine environments is critical to predict the toxicological impacts of worldwide explosive-contaminated sites adjacent to estuaries, wetlands, and the coastal ocean. Marine sediments have been identified as sites of enhanced munitions removal, yet most studies addressing these interactions focus on soils and freshwater sediments. The present study measured the kinetics of 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) sorption onto 2 marine sediments of varying grain sizes (silt vs sand) and organic carbon (OC) content. Abiotic sediment sorption tests were performed at 23 °C, 15 °C, and 4 °C by spiking TNT and RDX solutions directly into anaerobic sediment slurries. Marine sediments showed significantly higher compound uptake rates (0.30-0.80 h(-1) ) than freshwater silt (0.0046-0.0065 h(-1) ) for both compounds, probably because of lower compound solubilities and a higher pH in marine systems. Equilibrium partition constants are on the same order of magnitude for marine silt (1.1-2.0 L kg(-1) sediment) and freshwater silt (1.4-3.1 L kg(-1) sediment) but lower for marine sand (0.72-0.92 L kg(-1) sediment). Total organic carbon content in marine sediments varied linearly with equilibrium partition constants for TNT and was moderately linear for RDX. Uptake rates and equilibrium constants of explosives are inversely correlated to temperature regardless of sediment type because of kinetic barriers associated with low temperatures. © 2015 SETAC.

Influence of soil organic matter composition on the partition of organic compounds

USGS Publications Warehouse

Rutherford, D.W.; Chiou, C.T.; Klle, D.E.

1992-01-01

The sorption at room temperature of benzene and carbon tetrachloride from water on three high-organic-content soils (muck, peat, and extracted peat) and on cellulose was determined in order to evaluate the effect of sorbent polarity on the solute partition coefficients. The isotherms are highly linear for both solutes on all the organic matter samples, which is consistent with a partition model. For both solutes, the extracted peat shows the greatest sorption capacity while the cellulose shows the lowest capacity; the difference correlates with the polar-to-nonpolar group ratio [(O + N)/C] of the sorbent samples. The relative increase of solute partition coefficient (Kom) with a decrease of sample polar content is similar for both solutes, and the limiting sorption capacity on a given organic matter sample is comparable between the solutes. This observation suggests that one can estimate the polarity effect of a sample of soil organic matter (SOM) on Kom of various nonpolar solutes by determining the partition coefficient of single nonpolar solute when compositional analysis of the SOM is not available. The observed dependence of Kom on sample polarity is used to account for the variation of Kom values of individual compounds on different soils that results from change in the polar group content of SOM. On the assumption that the carbon content of SOM in "ordinary soils" is 53-63%, the calculated variation of Kom is a factor of ???3. This value is in agreement with the limit of variation of most Kom data with soils of relatively high SOM contents.

Size distribution and sorption of polychlorinated biphenyls during haze episodes

NASA Astrophysics Data System (ADS)

Zhu, Qingqing; Liu, Guorui; Zheng, Minghui; Zhang, Xian; Gao, Lirong; Su, Guijin; Liang, Yong

2018-01-01

There is a lack of studies on the size distribution of polychlorinated biphenyls (PCBs) during haze days, and their sorption mechanisms on aerosol particles remain unclear. In this study, PCBs in particle-sized aerosols from urban atmospheres of Beijing, China were investigated during haze and normal days. The concentrations, gas/particle partitioning, size distribution, and associated human daily intake of PCBs via inhalation were compared during haze days and normal days. Compared with normal days, higher particle mass-associated PCB levels were measured during haze days. The concentrations of ∑PCBs in particulate fractions were 11.9-134 pg/m3 and 6.37-14.9 pg/m3 during haze days and normal days, respectively. PCBs increased with decreasing particle size (>10 μm, 10-2.5 μm, 2.5-1.0 μm, and ≤1.0 μm). During haze days, PCBs were overwhelmingly associated with a fine particle fraction of ≤1.0 μm (64.6%), while during normal days the contribution was 33.7%. Tetra-CBs were the largest contributors (51.8%-66.7%) both in the gas and particle fractions during normal days. The profiles in the gas fraction were conspicuously different than those in the PM fractions during haze days, with di-CBs predominating in the gas fraction and higher homologues (tetra-CBs, penta-CBs, and hexa-CBs) concurrently accounting for most of the PM fractions. The mean-normalized size distributions of particulate mass and PCBs exhibited unimodal patterns, and a similar trend was observed for PCBs during both days. They all tended to be in the PM fraction of 1.0-2.5 μm. Adsorption might be the predominating mechanism for the gas-particle partitioning of PCBs during haze days, whereas absorption might be dominative during normal days.

Fibers and materials of medical application

NASA Technical Reports Server (NTRS)

Fridman, L. I.

1993-01-01

Efferent sorption methods of organism detoxication (by medical trend) are presented. Recently, specialists have shown their keen interest in the problem of treating exogenous and endogenous intoxications. This was stipulated by the growing production and accumulation of chemical products for industrial, agricultural, and domestic needs. To solve this problem the industrial production of carbon fibrous adsorbents was developed and implemented at NII Chimvolokno in St. Petersburg. A description of the carbon fibers is given. Also, application of modern composite materials for manufacturing compression-distraction apparatus used for setting fractured bones is described.

Cation mobility and the sorption of chloroform in zeolite NaY: molecular dynamics study.

PubMed

Ramsahye, Naseem A; Bell, Robert G

2005-03-17

Molecular dynamics simulations at temperatures of 270, 330, and 390 K have been carried out to address the question of cation migration upon chloroform sorption in sodium zeolite Y. The results show that sodium cations located in different sites exhibit different types of mobility. These may be summarized as follows: (1) SII cations migrate toward the center of the supercage upon sorption, due to interactions with the polar sorbate molecules. (2) SI' cations hop from the sodalite cage into the supercage to fill vacant SII sites. (3) SI' cations migrate to other SI' sites within the same sodalite cage. (4) SI cations hop out of the double six-rings into SI' sites. In some instances, concerted motion of cations is observed. Furthermore, former SI' and SI cations, having crossed to SII sites, may then further migrate within the supercage, as in (1). The cation motion is dependent on the level of sorbate loading, with 10 molecules per unit cell not being enough to induce significant cation displacements, whereas the sorption of 40 molecules per unit cell results in a number of cations being displaced from their original positions. Further rearrangement of the cation positions is observed upon evacuation of the simulation cell, with some cations reverting back to sites normally occupied in bare NaY.

Optimization of Nano-Carbon Materials for Hydrogen Sorption

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yakobson, Boris I

2013-08-02

Research undertaken has added to the understanding of several critical areas, by providing both negative answers (and therefore eliminating expensive further studies of unfeasible paths) and positive feasible options for storage. Theoretical evaluation of the early hypothesis of storage on pure carbon single wall nanotubes (SWNT) has been scrutinized with the use of comprehensive computational methods (and experimental tests by the Center partners), and demonstrated that the fundamentally weak binding energy of hydrogen is not sufficiently enhanced by the SWNT curvature or even defects, which renders carbon nanotubes not practical media. More promising direction taken was towards 3-dimensional architectures ofmore » high porosity where concurrent attraction of H2 molecule to surrounding walls of nano-scale cavities can double or even triple the binding energy and therefore make hydrogen storage feasible even at ambient or somewhat lower temperatures. An efficient computational tool has been developed for the rapid capacity assessment combining (i) carbon-foam structure generation, (ii) accurate empirical force fields, with quantum corrections for the lightweight H2, and (iii) grand canonical Monte Carlo simulation. This made it possible to suggest optimal designs for carbon nanofoams, obtainable via welding techniques from SWNT or by growth on template-zeolites. As a precursor for 3D-foams, we have investigated experimentally the synthesis of VANTA (Vertically Aligned NanoTube Arrays). This can be used for producing nano-foams. On the other hand, fluorination of VANTA did not show promising increase of hydrogen sorption in several tests and may require further investigation and improvements. Another significant result of this project was in developing a fundamental understanding of the elements of hydrogen spillover mechanisms. The benefit of developed models is the ability to foresee possible directions for further improvement of the spillover mechanism.« less

Long residence times of rapidly decomposable soil organic matter: application of a multi-phase, multi-component, and vertically resolved model (BAMS1) to soil carbon dynamics

NASA Astrophysics Data System (ADS)

Riley, W. J.; Maggi, F.; Kleber, M.; Torn, M. S.; Tang, J. Y.; Dwivedi, D.; Guerry, N.

2014-07-01

Accurate representation of soil organic matter (SOM) dynamics in Earth system models is critical for future climate prediction, yet large uncertainties exist regarding how, and to what extent, the suite of proposed relevant mechanisms should be included. To investigate how various mechanisms interact to influence SOM storage and dynamics, we developed an SOM reaction network integrated in a one-dimensional, multi-phase, and multi-component reactive transport solver. The model includes representations of bacterial and fungal activity, multiple archetypal polymeric and monomeric carbon substrate groups, aqueous chemistry, aqueous advection and diffusion, gaseous diffusion, and adsorption (and protection) and desorption from the soil mineral phase. The model predictions reasonably matched observed depth-resolved SOM and dissolved organic matter (DOM) stocks and fluxes, lignin content, and fungi to aerobic bacteria ratios. We performed a suite of sensitivity analyses under equilibrium and dynamic conditions to examine the role of dynamic sorption, microbial assimilation rates, and carbon inputs. To our knowledge, observations do not exist to fully test such a complicated model structure or to test the hypotheses used to explain observations of substantial storage of very old SOM below the rooting depth. Nevertheless, we demonstrated that a reasonable combination of sorption parameters, microbial biomass and necromass dynamics, and advective transport can match observations without resorting to an arbitrary depth-dependent decline in SOM turnover rates, as is often done. We conclude that, contrary to assertions derived from existing turnover time based model formulations, observed carbon content and Δ14C vertical profiles are consistent with a representation of SOM consisting of carbon compounds with relatively fast reaction rates, vertical aqueous transport, and dynamic protection on mineral surfaces.

Modeling study of natural emissions, source apportionment, and emission control of atmospheric mercury

NASA Astrophysics Data System (ADS)

Shetty, Suraj K.

Mercury (Hg) is a toxic pollutant and is important to understand its cycling in the environment. In this dissertation, a number of modeling investigations were conducted to better understand the emission from natural surfaces, the source-receptor relationship of the emissions, and emission reduction of atmospheric mercury. The first part of this work estimates mercury emissions from vegetation, soil and water surfaces using a number of natural emission processors and detailed (LAI) Leaf Area Index data from GIS (Geographic Information System) satellite products. East Asian domain was chosen as it contributes nearly 50% of the global anthropogenic mercury emissions into the atmosphere. The estimated annual natural mercury emissions (gaseous elemental mercury) in the domain are 834 Mg yr-1 with 462 Mg yr-1 contributing from China. Compared to anthropogenic sources, natural sources show greater seasonal variability (highest in simmer). The emissions are significant, sometimes dominant, contributors to total mercury emission in the regions. The estimates provide possible explanation for the gaps between the anthropogenic emission estimates based on activity data and the emission inferred from field observations in the regions. To understand the contribution of domestic emissions to mercury deposition in the United States, the second part of the work applies the mercury model of Community Multi-scale Air Quality Modeling system (CMAQ-Hg v4.6) to apportion the various emission sources attributing to the mercury wet and dry deposition in the 6 United States receptor regions. Contributions to mercury deposition from electric generating units (EGU), iron and steel industry (IRST), industrial point sources excluding EGU and IRST (OIPM), the remaining anthropogenic sources (RA), natural processes (NAT), and out-of-boundary transport (BC) in domain was estimated. The model results for 2005 compared reasonably well to field observations made by MDN (Mercury Deposition Network) and CAMNet (Canadian Atmospheric Mercury Measurement Network). The model estimated a total deposition of 474 Mg yr-1 to the CONUS (Contiguous United States) domain, with two-thirds being dry deposited. Reactive gaseous mercury contributed the most to 60% of deposition. Emission speciation distribution is a key factor for local deposition as contribution from large point sources can be as high as 75% near (< 100 km) the emission sources, indicating that emission reduction may result in direct deposition decrease near the source locations. Among the sources, BC contributes to about 68% to 91% of total deposition. Excluding the BC's contribution, EGU contributes to nearly 50% of deposition caused by CONUS emissions in the Northeast, Southeast and East Central regions, while emissions from natural processes are more important in the Pacific and West Central regions (contributing up to 40% of deposition). The modeling results implies that implementation of the new emission standards proposed by USEPA (United States Environmental Protection Agency) would significantly benefit regions that have larger contributions from EGU sources. Control of mercury emissions from coal combustion processes has attracted great attention due to its toxicity and the emission-control regulations and has lead to advancement in state-of-the-art control technologies that alleviate the impact of mercury on ecosystem and human health. This part of the work applies a sorption model to simulate adsorption of mercury in flue gases, onto a confined-bed of activated carbon. The model's performances were studied at various flue gas flow rates, inlet mercury concentrations and adsorption bed temperatures. The process simulated a flue gas, with inlet mercury concentration of 300 ppb, entering at a velocity of 0.3 m s-1 from the bottom into a fixed bed (inside bed diameter of 1 m and 3 m bed height; bed temperature of 25 °C) of activated carbon (particle size of 0.004 m with density of 0.5 g cm-3 and surface area of 90.25 cm2 g -1). The model result demonstrated that a batch of activated carbon bed was capable of controlling mercury emission for approximately 275 days after which further mercury uptake starts to decrease till it reaches about 500 days when additional control ceases. An increase in bed temperature significantly reduces mercury sorption capacity of the activated carbon. Increase in flue gas flow rate may result in faster consumption of sorption capacity initially but at a later stage, the sorption rate decreases due to reduced sorption capacity. Thus, overall sorption rate remains unaffected. The activated carbon's effective life (time to reach saturation) is not affected by inlet mercury concentration, implying that the designing and operation of a mercury sorption process can be done independently. The results provide quantitative indication for designing efficient confined-bed process to remove mercury from flue gases.

Analytical Aspects Relating to the Estimation of Carbon Filter Performance for Military Applications

DTIC Science & Technology

2013-07-01

materials having relatively low room-temperature vapor pressures and exhibiting Type I Brunauer, Edward, and Teller (BET) isotherms . Many compounds that...47 7.2.4 Breakthrough Time Relationship ...................................................49 7.3 Sorption of...various flow rates (from ref 3) ......51 10. Illustration of BET isotherm types (from ref 6) .........................................58 11

ARSENATE AND ARSENITE REMOVAL BY ZERO-VALENT IRON: EFFECTS OF PHOSPHATE, SILICATE, CARBONATE, BORATE, SULFATE, CHROMATE, MOLYBDATE, AND NITRATE, RELATIVE TO CHLORIDE

EPA Science Inventory

Batch tests were performed to evaluate the effects of inorganic anion competition on the kinetics of arsenate (As(V)) and arsenite (As(III)) removal by zerovalent iron (Peerless Fe0) in aqueous solution. The oxyanions underwent either sorption-dominated reactions (phosphate, sil...

Glassy Carbons

DTIC Science & Technology

1975-02-01

size is polydisperse. A controlled variation of the dispersion would be useful in tailoring properties, particularly in chemical ab- sorption and...20 10.8 ,, V-10-42 14.8 ---- PFA -2000 13.1 13.0 H-54 12.2 of Our Sample # 311-19(750) 5.0-65 Polydisperse312-10(2000) 19.7-53 of 312-31(2000) 14.2-65

Sorption of lead by settling pond soils after reclamation treatments

NASA Astrophysics Data System (ADS)

Asensio, Verónica; Forján, Rubén; Vega, Flora A.; Andrade, Luisa; Covelo, Emma F.

2013-04-01

The reclamation of degraded soils adding waste amendments can add significant concentrations of Pb. Because of this, it is important to know the sorption capacity of Pb by the soils where wastes with high concentrations of this metal are applied. To determine the sorption capacity of Pb by mine soils, before and after reclamation treatments, four different sites were selected at a settling pond mine zone: an untreated one as the control sample (B1), a vegetated one with pines for 21 years (B2v), a vegetated with eucalyptus for 6 years (B3v) and an amended with sewage sludges and paper mill residues for 5 months (B4w). All soils had one horizon except B4w, where twice were sampled (B4Aw and B4Bw). The B4Bw is considered analogous of the control soil. To evaluate the sorption capacity by the soils, sorption isotherms were constructed using single-metal solutions of Pb2+ nitrates (0.03, 0.05, 0.08, 0.1 and 0.5 mmol L-1) containing 0.01 M NaNO3 as background electrolyte (Vega et al., 2009). The overall capacity of the soil to sorb Pb was evaluated as the slope Kr (Vega et al., 2008). The obtained results show that the sorption isotherm of Pb by control soil (B1) and its analogous (B4Bw) are of L-type curve, whereas the sorption isotherms of the treated soils (B2v, B3v and B4Aw) are of H-type curve (Giles et al., 1974). The most of the obtained isotherms do not fit with the models of Langmuir or Freundlich, therefore sorption capacity was evaluated by Kr parameter. According to the obtained Kr parameter, B1 and B4Bw have the lowest Pb sorption capacity (Kr = 0.480 and 0.556, respectively), which increased two times after recently waste amending (B4Aw; Kr = 0.998). The vegetated sites (B2v and B3v) also have higher sorption capacity than B1, but lower than B4Aw (Kr = 0.692 and 0.725, respectively). The highest sorption capacity of Pb by the amended soil is due to its characteristics such as high pH and organic carbon content. This is corroborated by the significantly positive correlation of Kr for Pb and the soil pH, effective cation exchange capacity (CECe), the different forms of C (inorganic, humin, fulvic and humic acids), the percentage of clay fraction and the percentage of crystalline minerals in that fraction (P < 0.01). Therefore, the best treatment to increase the sorption capacity of Pb by mine soils is the amendment with organic wastes. References Giles, C.H.; Smith, D.; Huitson, A. 1974. J. Colloid. Interface Sci. 47: 755-756. Vega, F.A.; Covelo, E.F.; Andrade, M.L. 2009. J. Hazard. Mater. 169: 36-45. Vega, F.A.; Covelo, E.F.; Andrade, M.L. 2008. J. Colloid. Interface Sci. 327: 275-286.

Benchscale Assessment of the Efficacy of a Reactive Core Mat to Isolate PAH-spiked Aquatic Sediments.

PubMed

Meric, Dogus; Barbuto, Sara; Sheahan, Thomas C; Shine, James P; Alshawabkeh, Akram N

2014-01-01

This paper describes the results of a benchscale testing program to assess the efficacy of a reactive core mat (RCM) for short term isolation and partial remediation of contaminated, subaqueous sediments. The 1.25 cm thick RCM (with a core reactive material such as organoclay with filtering layers on top and bottom) is placed on the sediment, and approximately 7.5 - 10 cm of overlying soil is placed on the RCM for stability and protection. A set of experiments were conducted to measure the sorption characteristics of the mat core (organoclay) and sediment used in the experiments, and to determine the fate of semi-volatile organic contaminants and non-reactive tracers through the sediment and reactive mat. The experimental study was conducted on naphthalene-spiked Neponset River (Milton, MA) sediment. The results show nonlinear sorption behavior for organoclay, with sorption capacity increasing with increasing naphthalene concentration. Neponset River sediment showed a notably high sorption capacity, likely due to the relatively high organic carbon fraction (14%). The fate and transport experiments demonstrated the short term efficiency of the reactive mat to capture the contamination that is associated with the post-capping period during which the highest consolidation-induced advective flux occurs, driving solid particles, pore fluid and soluble contaminants toward the reactive mat. The goal of the mat placement is to provide a physical filtering and chemically reactive layer to isolate contamination from the overlying water column. An important finding is that because of the high sorption capacity of the Neponset River sediment, the physical filtering capability of the mat is as critical as its chemical reactive capacity.

Attenuation and colloidal mobilization of bacteriophages in natural sediments under anoxic as compared to oxic conditions.

PubMed

Klitzke, Sondra; Schroeder, Jendrik; Selinka, Hans-Christoph; Szewzyk, Regine; Chorus, Ingrid

2015-06-15

Redox conditions are known to affect the fate of viruses in porous media. Several studies report the relevance of colloid-facilitated virus transport in the subsurface, but detailed studies on the effect of anoxic conditions on virus retention in natural sediments are still missing. Therefore, we investigated the fate of viruses in natural flood plain sediments with different sesquioxide contents under anoxic conditions by considering sorption to the solid phase, sorption to mobilized colloids, and inactivation in the aqueous phase. Batch experiments were conducted under oxic and anoxic conditions at pH values between 5.1 and 7.6, using bacteriophages MS2 and PhiX174 as model viruses. In addition to free and colloid-associated bacteriophages, dissolved and colloidal concentrations of Fe, Al and organic C as well as dissolved Ca were determined. Results showed that regardless of redox conditions, bacteriophages did not adsorb to mobilized colloids, even under favourable charge conditions. Under anoxic conditions, attenuation of bacteriophages was dominated by sorption over inactivation, with MS2 showing a higher degree of sorption than PhiX174. Inactivation in water was low under anoxic conditions for both bacteriophages with about one log10 decrease in concentration during 16 h. Increased Fe/Al concentrations and a low organic carbon content of the sediment led to enhanced bacteriophage removal under anoxic conditions. However, even in the presence of sufficient Fe/A-(hydr)oxides on the solid phase, bacteriophage sorption was low. We presume that organic matter may limit the potential retention of sesquioxides in anoxic sediments and should thus be considered for the risk assessment of virus breakthrough in the subsurface. Copyright © 2015 Elsevier B.V. All rights reserved.

Sorption interactions of organic compounds with soils affected by agricultural olive mill wastewater.

PubMed

Keren, Yonatan; Borisover, Mikhail; Bukhanovsky, Nadezhda

2015-11-01

The organic compound-soil interactions may be strongly influenced by changes in soil organic matter (OM) which affects the environmental fate of multiple organic pollutants. The soil OM changes may be caused by land disposal of various OM-containing wastes. One unique type of OM-rich waste is olive mill-related wastewater (OMW) characterized by high levels of OM, the presence of fatty aliphatics and polyphenolic aromatics. The systematic data on effects of the land-applied OMW on organic compound-soil interactions is lacking. Therefore, aqueous sorption of simazine and diuron, two herbicides, was examined in batch experiments onto three soils, including untreated and OMW-affected samples. Typically, the organic compound-soil interactions increased following the prior land application of OMW. This increase is associated with the changes in sorption mechanisms and cannot be attributed solely to the increase in soil organic carbon content. A novel observation is that the OMW application changes the soil-sorbent matrix in such a way that the solute uptake may become cooperative or the existing ability of a soil sorbent to cooperatively sorb organic molecules from water may become characterized by a larger affinity. The remarkable finding of this study was that in some cases a cooperative uptake of organic molecules by soils makes itself evident in distinct sigmoidal sorption isotherms rarely observed in soil sorption of non-ionized organic compounds; the cooperative herbicide-soil interactions may be characterized by the Hill model coefficients. However, no single trend was found for the effect of applied OMW on the mechanisms of organic compound-soil interactions. Copyright © 2015 Elsevier Ltd. All rights reserved.

Usefulness of Mehlich-3 test in the monitoring of phosphorus dispersion from Polish arable soils.

PubMed

Szara, Ewa; Sosulski, Tomasz; Szymańska, Magdalena; Szyszkowska, Katarzyna

2018-04-19

A considerable area of soils with low abundance of plant-available phosphorus and relatively low consumption of phosphorus fertilisers recorded in Poland over the last 20-25 years suggests that the dispersion of phosphates from arable soils in Poland can be low. The literature, however, provides reports on a considerable share of Polish agriculture in phosphorus pollution of Baltic Sea waters. The literature provides no data concerning phosphorus sorption parameters of arable soils in Poland. Due to this, the study involved the analysis of sorption properties: 1-point phosphorus sorption index (PSI) and degree of phosphorus saturation, based on molar ratio P, Al, and Fe determined by the Mehlich-3 method (DPS-1 M3  = P / (Al + Fe) and DPS-2 M3  = P / Al), 59 soils representing the main types of texture of soils in Poland, characterised by variable content of plant-available phosphorus by Egner-Riehm DL, organic carbon, and soil pH. The obtained results suggest that the soil texture has a lower effect on sorption properties (PSI) than the degree of acidification. Sorption parameters of soils increased with soil acidification as a result of an increase in the content of Al and Fe extracted by the Mehlich-3 extract in strongly acidified soils. An important finding of our study was evidencing that within the same class of abundance in plant-available phosphorus, the soils varied in the degree of phosphorus saturation and content of active phosphorus. This suggests the possibility of losses of phosphorus even from soils with low abundance of the component provided they are characterised by a high value of parameters DPS-1 M3 and DPS-2 M3 .

Mucilage from seeds of chia (Salvia hispanica L.) used as soil conditioner; effects on the sorption-desorption of four herbicides in three different soils.

PubMed

Di Marsico, A; Scrano, L; Amato, M; Gàmiz, B; Real, M; Cox, L

2018-06-01

The objective of this work was to determine the effect of the mucilage extracted from Chia seeds (Salvia hispanica L.) as soil amendment on soil physical properties and on the sorption-desorption behaviour of four herbicides (MCPA, Diuron, Clomazone and Terbuthylazine) used in cereal crops. Three soils of different texture (sandy-loam, loam and clay-loam) were selected, and mercury intrusion porosimetry and surface area analysis were used to examine changes in the microstructural characteristics caused by the reactions that occur between the mucilage and soil particles. Laboratory studies were conducted to characterise the selected herbicides with regard their sorption on tested soils added or not with the mucilage. Mucilage amendment resulted in a reduction in soil porosity, basically due to a reduction in larger pores (radius>10μm) and an important increase in finer pores (radius<10μm) and in partcles' surface. A higher herbicide sorption in the amended soils was ascertained when compared to unamended soils. The sorption percentage of herbicides in soils treated with mucilage increased in the order; sandy-loam

Determination of soil–water sorption coefficients of volatile methylsiloxanes

PubMed Central

Kozerski, Gary E; Xu, Shihe; Miller, Julie; Durham, Jeremy

2014-01-01

The sorption behaviors of 4 cyclic and linear volatile methyl siloxane (VMS) compounds between water and organic matter in 3 United Kingdom soils were studied by a batch equilibrium method using13C-enriched sorbates. Sorption and desorption kinetics and isotherms were determined for octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), octamethyltrisiloxane (L3), and decamethyltetrasiloxane (L4). Concentrations of [13C]-VMS in the soil and aqueous phases were measured directly by extraction and gas chromatography–mass spectrometry techniques. All VMS compounds were sorbed rapidly, reaching constant distributions in all soils by 24 h. Desorption kinetics were very rapid, with reattainment of equilibrium within 1 h. In the main, linear isotherms were observed for aqueous concentrations at or below 4% of the solubility limits. The average sorption organic carbon partition coefficient (log KOC) values across soils were 4.23 for D4, 5.17 for D5, 4.32 for L3, and 5.13 for L4, with standard deviations of 0.09 to 0.34. Desorption KOC values were systematically greater by 0.1 log units to 0.3 log units. The linear isotherms and low variation in KOC values across soils suggested partitioning-dominated sorption of the VMS. Compared with traditional hydrophobic organic compounds, KOC values for the VMS compounds were significantly lower than expected on the basis of their octanol–water partition coefficients. A linear free energy relationship analysis showed that these differences could be rationalized quantitatively in terms of the inherent characteristics of the VMS compounds, combined with the differences in solvation properties of organic matter and octanol. Environ Toxicol Chem 2014; 33:1937–1945. PMID:24862578

Sorption of Pharmaceuticals, Heavy Metals, and Herbicides to Biochar in the Presence of Biosolids.

PubMed

Bair, Daniel A; Mukome, Fungai N D; Popova, Inna E; Ogunyoku, Temitope A; Jefferson, Allie; Wang, Daoyuan; Hafner, Sarah C; Young, Thomas M; Parikh, Sanjai J

2016-11-01

Agricultural practices are increasingly incorporating recycled waste materials, such as biosolids, to provide plant nutrients and enhance soil functions. Although biosolids provide benefits to soil, municipal wastewater treatment plants receive pharmaceuticals and heavy metals that can accumulate in biosolids, and land application of biosolids can transfer these contaminants to the soil. Environmental exposure of these contaminants may adversely affect wildlife, disrupt microbial communities, detrimentally affect human health through long-term exposure, and cause the proliferation of antibiotic-resistant bacteria. This study considers the use of biochar co-amendments as sorbents for contaminants from biosolids. The sorption of pharmaceuticals (ciprofloxacin, triclocarban, triclosan), and heavy metals (Cu, Cd, Ni, Pb) to biochars and biochar-biosolids-soil mixtures was examined. Phenylurea herbicide (monuron, diuron, linuron) sorption was also studied to determine the potential effect of biochar on soil-applied herbicides. A softwood (SW) biochar (510°C) and a walnut shell (WN) biochar (900°C) were used as contrasting biochars to highlight potential differences in biochar reactivity. Kaolinite and activated carbon served as mineral and organic controls. Greater sorption for almost all contaminants was observed with WN biochar over SW biochar. The addition of biosolids decreased sorption of herbicides to SW biochar, whereas there was no observable change with WN biochar. The WN biochar showed potential for reducing agrochemical and contaminant transport but may inhibit the efficacy of soil-applied herbicides. This study provides support for minimizing contaminant mobility from biosolids using biochar as a co-amendment and highlights the importance of tailoring biochars for specific characteristics through feedstock selection and pyrolysis-gasification conditions. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Sorption-desorption equilibrium and diffusion of tetracycline in poultry litter and municipal biosolids soil amendments.

PubMed

D'Angelo, E

2017-12-01

Tetracycline (TET) is commonly used to treat bacterial diseases in humans and chickens (Gallus gallus domesticus), is largely excreted, and is found at elevated concentrations in treated sewage sludge (biosolids) and poultry litter (excrement plus bedding materials). Routine application of these nutrient-and carbon-enriched materials to soils improves fertility and other characteristics, but the presence of antibiotics (and other pharmaceuticals) in amendments raises questions about potential adverse effects on biota and development of antibiotic resistance in the environment. Hazard risks are largely dictated by sorption-desorption and diffusion behavior in amendments, so these processes were evaluated from sorption-desorption equilibrium isotherm and diffusion cell experiments with four types amendments (biosolids, poultry manure, wood chip litter, and rice hull litter) at three temperatures (8 °C, 20 °C and 32 °C). Linear sorption-desorption equilibrium distribution constants (Kd) in native amendments ranged between 124-2418 L kg -1 . TET sorption was significantly increased after treatment with alum, and there was a strong exponential relationship between Kd and the concentration of bound Al 3+ in amendments (R 2  = 0.94), which indicated that amendments contained functional groups capable of chelating Al 3+ and forming metal bridges with TET. Effective diffusion coefficients of TET in amendments ranged between 0.1 and 5.2 × 10 -6  cm 2  s -1 , which were positively related to temperature and inversely related to Kd by a multiple regression model (R 2  = 0.86). Treatment of organic amendments with alum greatly increased Kd, would decrease D s , and so would greatly reduce hazard risks of applying these organic amendments with this antibiotic to soils. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorptive and desorptive fractionation of dissolved organic matter by mineral soil matrices.

PubMed

Oren, Adi; Chefetz, Benny

2012-01-01

Interactions of dissolved organic matter (DOM) with soil minerals, such as metal oxides and clays, involve various sorption mechanisms and may lead to sorptive fractionation of certain organic moieties. While sorption of DOM to soil minerals typically involves a degree of irreversibility, it is unclear which structural components of DOM correspond to the irreversibly bound fraction and which factors may be considered determinants. To assist in elucidating that, the current study aimed at investigating fractionation of DOM during sorption and desorption processes in soil. Batch DOM sorption and desorption experiments were conducted with organic matter poor, alkaline soils. Fourier-transform infrared (FTIR) and UV-Vis spectroscopy were used to analyze bulk DOM, sorbed DOM, and desorbed DOM fractions. Sorptive fractionation resulted mainly from the preferential uptake of aromatic, carboxylic, and phenolic moieties of DOM. Soil metal-oxide content positively affected DOM sorption and binding of some specific carboxylate and phenolate functional groups. Desorptive fractionation of DOM was expressed by the irreversible-binding nature of some carboxylic moieties, whereas other bound carboxylic moieties were readily desorbed. Inner-sphere, as opposed to outer-sphere, ligand-exchange complexation mechanisms may be responsible for these irreversible, as opposed to reversible, interactions, respectively. The interaction of aliphatic DOM constituents with soil, presumably through weak van der Waals forces, was minor and increased with increasing proportion of clay minerals in the soil. Revealing the nature of DOM-fractionation processes is of great importance to understanding carbon stabilization mechanisms in soils, as well as the overall fate of contaminants that might be associated with DOM. Copyright © by the American Society of Agronomy, Crop Science Society of America, and Soil Science Society of America, Inc.

Characterization of potassium hydroxide (KOH) modified hydrochars from different feedstocks for enhanced removal of heavy metals from water.

PubMed

Sun, Kejing; Tang, Jingchun; Gong, Yanyan; Zhang, Hairong

2015-11-01

Hydrochars produced from different feedstocks (sawdust, wheat straw, and corn stalk) via hydrothermal carbonization (HTC) and KOH modification were used as alternative adsorbents for aqueous heavy metals remediation. The chemical and physical properties of the hydrochars and KOH-treated hydrochars were characterized, and the ability of hydrochars for removal of heavy metals from aqueous solutions as a function of reaction time, pH, and initial contaminant concentration was tested. The results showed that KOH modification of hydrochars might have increased the aromatic and oxygen-containing functional groups, such as carboxyl groups, resulting in about 2-3 times increase of cadmium sorption capacity (30.40-40.78 mg/g) compared to that of unmodified hydrochars (13.92-14.52 mg/g). The sorption ability among different feedstocks after modification was as the following: sawdust > wheat straw > corn stack. Cadmium sorption kinetics on modified hydrochars could be interpreted with a pseudo-second order, and sorption isotherm was simulated with Langmuir adsorption model. High cadmium uptake on modified hydrochars was observed over the pH range of 4.0-8.0, while for other heavy metals (Pb(2+), Cu(2+), and Zn(2+)) the range was 4.0-6.0. In a multi-metal system, the sorption capacity of heavy metals by modified hydrochars was also higher than that by unmodified ones and followed the order of Pb(II) > Cu(II) > Cd(II) > Zn(II). The results suggest that KOH-modified hydrochars can be used as a low cost, environmental-friendly, and effective adsorbent for heavy metal removal from aqueous solutions.

CO2 sorption on surface-modified carbonaceous support: Probing the influence of the carbon black microporosity and surface polarity

NASA Astrophysics Data System (ADS)

Gargiulo, Valentina; Alfè, Michela; Ammendola, Paola; Raganati, Federica; Chirone, Riccardo

2016-01-01

The use of solid sorbents is a convenient option in post-combustion CO2 capture strategies. Sorbents selection is a key point because the materials are required to be both low-cost and versatile in typical post-combustion conditions in order to guarantee an economically advantageous overall process. This work compares strategies to tailor the chemico-physical features of carbon black (CB) by surface-modification and/or coating with a CO2-sorbent phase. The influence of the CB microporosity, enhanced by chemical/thermal treatments, is also taken into account. Three CB surface modifications are performed and compared: (i) oxidation and functionalization with amino-groups, (ii) coating with iron oxides and (iii) impregnation with an ionic liquid (IL). The CO2 capture performance is evaluated on the basis of the breakthrough curves measured at atmospheric pressure and room temperature in a lab-scale fixed bed micro-reactor. Most of tested solids adsorb a CO2 amount significantly higher than a 13X zeolite and DARCO FGD (Norit) activated carbon (up to 4 times more in the best case). The sorbents bearing basic functionalities (amino-groups and IL) exhibit the highest CO2 sorption capacity. The use of a microporous carbonaceous support limits the accessibility of CO2 toward the adsorbing phase (IL or FM) lowering the number of accessible binding sites for CO2.