Biomedical subjects

Benny Chefetz

Publications and source records attributed to Benny Chefetz.

13 recordsLinked to original sources

PubMed2006

The role of lipids on sorption characteristics of freshwater- and wastewater-irrigated soils.

The soil lipid fraction can play an important role in the sorption of organic compounds. In this study, the impact of the lipid fraction of freshwater- and wastewater-irrigated soils on the sorption of non- and relatively polar compounds was assessed. Lipid analyses revealed a clear difference between the two lipid fractions. The lipid extract from the wastewater-irrigated soil was consistent with mainly straight paraffinic chain materials; the lipid extract from freshwater-irrigated soil, on the other hand, exhibited stronger signals of aromatics, double bonds, ester, ether, and methyl, in addition to a smaller contribution from methylene protons. Our data suggest that lipid removal induced a stronger increase in the soil's sorption affinity for solutes capable of polar interactions such as atrazine (2-chloro-4-ethylamino-6-isopropylamino-1,3,5-triazine) and chlorotoluron (N'-(3-chloro-4-methylphenyl)-N,N-dimethylurea) as compared to phenanthrene. Moreover, the level of increase in sorption affinities due to lipid removal was much higher for the freshwater-irrigated soil than for its wastewater-irrigated counterpart, even though the level of lipids in the freshwater-irrigated soil was half that in the wastewater-irrigated one (6 vs. 11% of the total organic C). The higher level of polar functionalities, such as ether and ester moieties, in the lipid fraction from the freshwater-irrigated soil suggests that these extractable compounds compete successfully with the polar solutes (atrazine and chlorotoluron) for specific binding sites in the soil organic matter (SOM). It appears that the composition of the lipid fraction may be a key consideration in unraveling the sorption of organic molecules in soils.

Adsorption↗

PubMed2006

Competitive sorption-desorption behavior of triazine herbicides with plant cuticular fractions.

Sorption interactions of plant cuticular matter with organic compounds are not yet fully understood. The objective of this study was to examine the competitive sorption-desorption interactions of the triazine herbicides (atrazine and ametryn) with cuticular fractions isolated from tomato fruits and leaves of Agave americana. The 13C NMR data suggest a rubber-like nature for the cutin. This biopolymer exhibited reversible and noncompetitive sorption. Enhanced desorption of atrazine was recorded in the bi-solute system with bulk and dewaxed A. americana cuticles. 13C NMR analyses of these samples suggested that the sorbed competitor ametryn facilitated a physical phase transition of rigid paraffinic sorption domain to mobile and flexible domain during sorption process. We suggest that the different sorption-desorption behavior obtained for the two cuticles is related to the higher content of waxes (14% vs 2.6%) and lower content of cutin (46% vs 75%) in the A. americana versus tomato fruit cuticle.

Absorption↗

PubMed2006

Interactions of sodium azide with triazine herbicides: effect on sorption to soils.

Sodium azide (NaN(3)) is one of the biocides commonly used to inhibit microbial growth during sorption experiments. However, a few reports have suggested that NaN(3) can react with the analyte of interest. In this study, the interactions of NaN(3) with triazine herbicides were investigated and the effect of atrazine transformation on its sorption to soil was evaluated. The concentration of atrazine in the presence of NaN(3) decreased significantly over period of time. After 14 days, only 38% of the initial atrazine concentration (10 mg l(-1)) was detected in a solution containing 1,000 mg l(-1) NaN(3) at pH 5.5. The magnitude and the rate of atrazine transformation increased with increase in NaN(3) load and with decrease in pH. In contrast to atrazine behavior, the concentrations of prometon and ametryn did not change during the experiment. GC/MS analysis indicated that the chlorine atom of atrazine is replaced by the azide group yielding 2-azido-4-(ethylamino)-6-(isopropylamino)-s-triazine. Atrazine transformation by NaN(3) significantly affected sorption of herbicide to soil. The presence of NaN(3) affects indirectly the sorption of atrazine due to competitive effect of its derivative. Our results demonstrated that the application of NaN(3) as a biocide in sorption-desorption experiments must be carefully evaluated. This issue is vital for sorption experiments conducted over long periods of time or/and with concentration of NaN(3) higher than 100 mg l(-1).

Adsorption↗

PubMed2005

Persistent organic pollutants and sedimentary organic matter properties: a case study in the Kishon River, Israel.

The Kishon River, the second largest coastal river in Israel, has been severely polluted for several decades. Sediments from upstream and downstream sites of the river were analyzed, lipid-extracted and evaluated for phenanthrene uptake. Total polycyclic aromatic hydrocarbon (PAH) concentration in downstream sediments was 299 microg kg(-1), consisting mostly of petrogenic-derived PAHs. Downstream sedimentary lipids were found to be dominated by fresh and decomposed petroleum-derived n-alkanes. The total PAH concentration in upstream sediments was 173 microg kg(-1), consisting mostly of pyrogenic-derived PAHs, whereas lipids from these sediments were mostly vegetation-derived. Spectroscopic data suggested an exceptionally high aromatic content in downstream humic acid, which originated from PAHs attached to its structure. Sorption data suggested that upstream sedimentary cuticle-derived lipids function as a sorption domain, while downstream sedimentary lipids, consisting of shorter-chain-length petroleum-derived alkanes, compete with phenanthrene for sorption sites.

Adsorption↗

PubMed2005

Sorption of polar and nonpolar aromatic organic contaminants by plant cuticular materials: role of polarity and accessibility.

In both forest and agricultural soils, plant derived cuticular materials can constitute a significant part of soil organic matter. In this study, the sorption of nonpolar (naphthalene and phenanthrene) and polar (phenol and 1-naphthol) aromatic organic pollutants to aliphatic-rich cuticularfractions of green pepper (Capsicum annuum) (i.e., bulk (PC1), dewaxed (PC2), nonsaponifiable (PC3), nonsaponifiable-nonhydrolyzable (PC4), and dewaxed-hydrolyzed residue (PC5)) were examined to better understand the influence of polarity and accessibility on their sorption behavior. The polarity and structures of cuticular fractions were characterized by elemental analysis, Fourier transform infrared spectroscopy, and solid-state 13C NMR. The sorption isotherms fit well to the Freundlich equation. Sorption of the tested organic compounds to PC4, which had more condensed domains, was nonlinear (Freundlich N(s) values of 0.766-0.966). For naphthalene and phenanthrene, the largest sorption capacity (K(oc)) occurred in PC5, which contained the highest paraffinic carbons (63%) and the lowest polarity: approximately 2 and aproximately 3 times higher than the respective carbon-normalized octanol-water partition coefficient (K(owc)), indicating that PC5 was a powerful sorption medium. For phenol and 1-naphthol, the largest K(oc) values occurred in PC4 with polar aromatic cores: approximattely 17 and approximately 7 times higher than the respective K(owc), suggesting that PC4 was much more accessible and compatible to polar aromatic pollutants than nonpolar aromatic pollutants. There was little or no correlation of K(oc) with either aliphatic or aromatic components of the tested aliphatic-rich sorbents because the polarity and accessibility apparently played a regulating role in the sorption of organic contaminants.

Adsorption↗

PubMed2005

Sorption-desorption behavior of polycyclic aromatic hydrocarbons in upstream and downstream river sediments.

Sorption and desorption behaviors of phenanthrene and naphthalene were studied with the whole sediment, humic acid (HA) and humin samples from downstream and upstream sites along the Kishon River, Israel. The 13C nuclear magnetic resonance spectra and the sorption coefficients suggest that sorption occurs to both aromatic and aliphatic moieties of the sedimentary organic matter and that rigid paraffinic domains probably contribute to the sorption non-linearity. The carbon-normalized Freundlich affinity values for the two sorbates were significantly higher for the whole sediment and humin samples from the downstream region of the river than for the upstream sediment samples. On the basis of the measured affinity values, the sorbents can be arranged in the following order: humin>HA>whole sediment. Phenanthrene exhibited the lowest desorption from the whole sediment samples compared with the other sorbents. For naphthalene, the desorption hysteresis obtained with the whole sediment and humin samples were similar: both exhibited a decrease in desorption with decreasing solute concentration. The higher sorption affinities observed for all the organic fractions from the downstream sediment are suggested to be related to the low levels of polar domains and humin content. It is concluded that in bulk sediment samples, the overall contribution of the HA fraction to short-term sorption is of high importance, but the sorption non-linearity is controlled mainly by the humin complexes. The low desorption potential recorded for the whole sediment samples could affect the natural attenuation of the sorbed hydrophobic organic compounds.

Adsorption↗

PubMed2005

Comparison of polycyclic aromatic hydrocarbon distributions and sedimentary organic matter characteristics in contaminated, coastal sediments from Pensacola Bay, Florida.

In this study, we examined the distribution of polycyclic aromatic hydrocarbons (PAHs) in a contaminated coastal area and the characteristics of the natural organic matter in tandem. We present a detailed study of PAH concentration, distribution, and organic matter characteristics of three core samples from Pensacola Bay, Florida. Solid-state 13C Nuclear Magnetic Resonance (NMR), pyrolysis gas chromatography coupled with mass spectrometry (GC-MS), and tetramethyl ammonium hydroxide (TMAH) thermochemolysis GC-MS were applied to obtain structural details about the sedimentary organic matter. Elemental compositions (carbon and nitrogen) and estimates of black carbon contents are also reported. These coastal sediments were found to contain more PAHs in the upper 15 cm layers than in the bottom 15-25 cm samples. The samples that contained the most PAHs also contained the least amount of aromatic carbon and contained a significant amount of paraffinic carbon. Lignin-derived pyrolysis and TMAH thermochemolysis products were abundant and generally higher in all of the samples in comparison to those reported for modern coastal sediments, indicating a large flux of terrestrial carbon. The black carbon contents were found to range from 4.3% to 6.8%, which are significantly lower than other reports of black carbon in sediments, which represent as much as 65% of the total organic carbon content. The low black carbon content suggests that this type of refractory carbon may not be as responsible for regulating PAH distribution as indicated by other researchers.

Carbon Isotopes↗

PubMed2004

Solid-state NMR characterization of pyrene-cuticular matter interactions.

One- and two-dimensional nuclear magnetic resonance (NMR) experiments were performed on Agave americana cutan and tomato cutin to examine the interactions between a hydrophobic pollutant, pyrene, and cuticular material. Variable-temperature NMR experiments show that cutan, an acid- and base-resistant cuticular biopolymer, undergoes the characteristic melting behavior of "polyethylene-like" crystallites, while the tomato cutin does not. The melting point of A. americana cutan was found to be approximately 360 K, which is consistent with the thickness of the polyethylene crystallites of 30-40 methylene units. Sorption models predict that the sorption behavior of hydrophobic pollutants should depend on the phase of the cuticular material. 13C NMR experiments on labeled pyrene were performed. The 13C T1 of pyrene decreases significantly from that of crystalline pyrene upon sorption to both tomato fruit cutin and A. americana cutan, indicating that the pyrene is mobile upon sorption. Magic angle spinning experiments at low spinning frequencies (2-4 kHz) provided the chemical shift anisotropy (CSA) parameters delta, the anisotropy, and eta, the asymmetry parameter, for crystalline and sorbed pyrene. For crystalline pyrene, two types of crystallographically distinctive pyrenes were observed. The first had delta = -97.4+/-0.5 ppm and eta = 0.934+/-0.006, while the second had delta = -98.1+/-0.5 ppm and eta = 0.823+/-0.008. After sorption to cutan, these CSA parameters were found to be delta = -78.9+/-5.3 ppm and eta < 0.70 independent of the length of time since completion of the sorption procedure. In tomato cutin, the CSA parameters were found to be dependent upon the time since completion of the sorption procedure. One and one-half months after sorption, delta was found to have a value of -30.4 ppm < delta < 0.0 ppm and eta was undeterminable, while after 22 months these values become delta = -80.0 +/-3.3 ppm and eta< 0.42. These changes in the CSA parameters demonstrate that upon sorption of pyrene to cutan, the pyrene undergoes anisotropic motion, while in cutin pyrene initially can tumble isotropically, but after 22 months this motion also becomes anisotropic. 2D heteronuclear correlation experiments indicate that pyrene is in close proximity to aliphatic cuticular materials after sorption. This work is directly relevant toward understanding the physical and chemical mechanisms of pollutant sorption to soil organic matter and, thus, help develop improved sorption models and pollution remediation techniques.

Adsorption↗

PubMed2004

Sorption-desorption behavior of triazine and phenylurea herbicides in Kishon river sediments.

Sorption and desorption hysteresis of widely applied triazine and phenylurea herbicides were studied for river sediments. Organic carbon normalized sorption coefficient (K(OC)) values for all herbicides were significantly higher for the sediment from the downstream region of the river vs. the upstream sediment. On the basis of the measured K(OC) values, the triazine herbicides can be arranged in the following order: terbutryn > terbuthylazine > ametryn > atrazine. Among the phenylurea herbicides, chlorotoluron exhibited higher sorption than isoproturon (K(OC) values of 137 vs. 60 and 228 vs. 125 L/kg for the upstream and downstream sediments, respectively). Moreover, chlorotoluron exhibited lower desorption potential as compared with isoproturon (apparent hysteresis index values were 0.2-0.3 for chlorotoluron vs. 0.6-0.9 for isoproturon, measured with the upstream sediment). High sorption affinity of chlorotoluron to the sediments is probably due to stronger H-bonding interactions of the herbicide molecules with the sorbents. For both phenylurea herbicides, desorption hysteresis increased with decrease in sorbed amount. This behavior was opposite to the hysteresis trend observed for the triazines. The Cl-triazines (atrazine and terbuthylazine) exhibited higher desorption hysteresis than the S-triazines (ametryn and terbutryn). Therefore, the apparent hysteresis index values calculated for the Cl-triazines were lower than the values of S-triazines (about 0.4 and 0.7, respectively). Based on the relative strength of H-bonding interactions of Cl- and S-triazines with formate anion and on the desorption hysteresis data we suggest a gradient-derived hole-filling sorption mechanism for the triazine herbicides with the river sediments.

Adsorption↗

PubMed2003

Sorption of phenanthrene and atrazine by plant cuticular fractions.

Several studies have shown selective preservation of plant cuticular materials in soils. However, very little is known about their function as sorbents for the hydrophobic organic contaminants (HOCs) in the soil. In this study, we investigated the sorption and desorption of phenanthrene and atrazine by cuticular fractions of pepper (bulk, dewaxed, nonsaponifiable, and nonhydrolyzable) to better understand the sorptive activity of cuticular matter in soils. The bulk and dewaxed cuticles exhibited carbon-normalized distribution coefficients (Koc) for phenanthrene and atrazine in the range of that reported for soil humic substances, although both samples were rich in aliphatic structures. No hysteresis was observed in the desorption isotherms of either solute. The nonhydrolyzable residue exhibited a very high Koc value for atrazine, whereas the nonsaponifiable sample be exhibited the lowest Koc value for both sorbates. Based on solubility parameter data, it is suggested that the nonsponifiable sample be considered an intermediate between the physical and chemical mixture of pectin and cutan/lignin-like fractions, whereas the dewaxed cuticle is a chemical blending of cutin and pectin. The n-hexane-normalized sorption data suggest that the pepper cuticle can interact specifically with atrazine. This study leads to the conclusion that the contribution of aliphatic-rich plant biopolymers to the sorption of HOCs can be significant because of their preservation and accumulation in soils.

Adsorption↗

PubMed2002

Phenanthrene sorption by aliphatic-rich natural organic matter.

Contaminant sorption, an important process that may limit bioavailability, hinder remediation, encourage environmental persistence, and control mobility in the environment, has been the focus of numerous studies. Despite these efforts, the fundamental understanding of sorptive processes in soil and sedimentary environments has not been resolved. For instance, many have suggested that contaminants, such as polycyclic aromatic hydrocarbons (PAHs), solely interact with aromatic domains of organic matter. Until now, studies have neglected the aliphatic components that are known to be a recalcitrant and significant part of soil and sedimentary organic matter (SOM). In this investigation, the sorption of phenanthrene to several aliphatic-rich SOM samples was measured. The samples included the following: SOM precursors (algae, degraded algae, cellulose, collagen, cuticle, and lignin), two kerogen samples, and a highly aromatic humic acid. All samples were characterized by cross polarization magic angle spinning carbon-13 (CPMAS 13C) NMR and carbon, hydrogen, and nitrogen analysis. Batch experiments demonstrated that the highest organic carbon normalized sorption coefficients (Koc values) were obtained with the Pula kerogen sample (log Koc = 4.88) that only contains 6.5% aromatic carbon. Other aliphatic-rich samples, namely the Green River kerogen, degraded algae, and collagen samples produced comparable log Koc values (4.64, 4.66, and 4.72, respectively) to that of the highly aromatic humic acid (log Koc = 4.67). Phenanthrene uptake was the least for cellulose and lignin, two major soil components. A comparison of phenanthrene Koc values and paraffinic carbon content revealed a positive correlation (Koc = 798 +/- 96.1 * paraffinic carbon (%), r2 = 0.56) and indicates that amorphous polymethylene carbon is an important consideration in phenanthrene sorption. This study establishes that aliphatic SOM domains have a strong affinity for phenanthrene and likely, other PAHs. Therefore, aliphatic structures, that are an important component of SOM, require more attention in the examination of sorption processes in terrestrial and sedimentary environments.

Adsorption↗

PubMedDate not supplied

Phenanthrene sorption to structurally modified humic acids.

Several studies emphasize the importance of soil organic matter characteristics in hydrophobic contaminant sorption and outline the strong dependence of sorption on organic matter aromaticity. In this study, the role of organic matter aromaticity in phenanthrene sorption was investigated using humic acids (HAs) from compost, peat, and soil that were structurally modified by bleaching, hydrolysis, oximation, and subcritical water extraction. The HAs were characterized with cross polarization magic angle spinning carbon-13 nuclear magnetic resonance (CPMAS 13C NMR) spectroscopy and used in batch equilibrations with phenanthrene. Bleaching substantially reduced the aromaticity of the samples whereas the other treatments increased the relative aromaticity. Phenanthrene sorption increased, even though there was a substantial reduction in sorbent aromaticity with some samples. The HAs that exhibited comparable CPMAS 13C NMR spectra and aromaticity did not behave similarly with respect to phenanthrene sorption. When the sorption data (K(oc) values) were correlated to sample aromaticity, the correlation coefficients (r2) did not exceed 0.39. Comparisons with the atomic H to C ratio provided slightly better r2 values (up to 0.54). This study demonstrates that macroscopic sorbent characteristics could not explain the observed phenanthrene sorption coefficients, aliphatic structural components of HAs can contribute appreciably to phenanthrene sorption, and organic matter physical conformation may regulate access to organic matter structures. Therefore, the use of only macroscopic sorbent properties, such as aromaticity, to predict and rationalize sorption values cannot solely be used to explain the behavior of organic contaminants in soil environments.

Adsorption↗

PubMedDate not supplied

Interactions of organic compounds with wastewater dissolved organic matter: role of hydrophobic fractions.

The role of structural fractions of dissolved organic matter (DOM) from wastewater in the sorption process of hydrophobic organic compounds is still not clear. In this study, DOM from two wastewater treatment plants (Lachish and Netanya, Israel) was fractionated to hydrophobic acid (HoA) and hydrophobic neutral (HoN) fractions. The fractions were characterized and their sorptive capabilities for s-triazine herbicides and polycyclic aromatic hydrocarbons (PAHs) were studied. For all sorbates, the binding to the HoN fractions was much higher than to HoA fractions. The HoA fractions were more polar than the HoN fractions, containing a higher level of carboxylic functionalities. However the higher binding coefficients of atrazine (2-chloro-4-ethylamine-6-isopropylamino-s-triazine) and ametryn [2-(ethylamino)-4-isopropylamino-6-methyl-thio-s-triazine] obtained for the HoN fractions suggest that their sorption is governed by hydrophobic-like interactions rather than H bonding. The values of binding coefficients of PAHs measured for the HoN fractions were within the range reported for humic acids and much higher than other fractions, suggesting that this fraction plays an important role in the overall sorption of these compounds by DOM. Higher sorption coefficients were measured for the Netanya DOM sample containing higher level of hydrophobic fractions (HoA + HoN) than the Lachish DOM, suggesting that the sorption of hydrophobic organic compounds by DOM is governed by the level of these structural substances. The evaluation of mobility of organic pollutants by wastewater irrigation requires not only assessment of the total carbon concentration but also, more importantly, the content of the hydrophobic fractions.

Adsorption↗