Is skin penetration a determining factor in skin sensitization ...

EPA Pesticide Factsheets

Summary:Background. It is widely accepted that substances that cannot penetrate through the skin will not be sensitisers. Thresholds based on relevant physicochemical parameters such as a LogKow > 1 and a MW 1 is a true requirement for sensitisation.Methods. A large dataset of substances that had been evaluated for their skin sensitisation potential, together with measured LogKow values was compiled from the REACH database. The incidence of skin sensitisers relative to non-skin sensitisers below and above the LogKow = 1 threshold was evaluated. Results. 1482 substances with associated skin sensitisation outcomes and measured LogKow values were identified. 305 substances had a measured LogKow < 0 and of those, 38 were sensitisers.Conclusions. There was no significant difference in the incidence of skin sensitisation above and below the LogKow = 1 threshold. Reaction chemistry considerations could explain the skin sensitisation observed for the 38 sensitisers with a LogKow < 0. The LogKow threshold is a self-evident truth borne out from the widespread misconception that the ability to efficiently penetrate the stratum corneum is a key determinant of skin sensitisation potential and potency. Using the REACH data extracted to test out the validity of common assumptions in the skin sensitization AOP. Builds on trying to develop a proof of concept IATA

Persistent organic pollutants (POPs) in a small, herbivorous, arctic marine zooplankton (Calanus hyperboreus): trends from April to July and the influence of lipids and trophic transfer.

PubMed

Fisk, A T; Stern, G A; Hobson, K A; Strachan, W J; Loewen, M D; Norstrom, R J

2001-01-01

Samples of Calanus hyperboreus, a herbivorous copepod, were collected (n = 20) between April and July 1998, and water samples (n = 6) were collected in May 1998, in the Northwater Polynya (NOW) to examine persistent organic pollutants (POPs) in a high Arctic marine zooplankton. Lipid content (dry weight) doubled, water content (r2 = 0.88) and delta15N (r2 = 0.54) significantly decreased, and delta13C significantly increased (r2 = 0.30) in the C. hyperboreus over the collection period allowing an examination of the role of these variables in POP dynamics in this small pelagic zooplankton. The rank and concentrations of POP groups in C. hyperboreus over the entire sampling was sum of PCB (30.1 +/- 4.03 ng/g, dry weight) > sum of HCH (11.8 +/- 3.23) > sum of DDT (4.74 +/- 0.74), sum of CHLOR (4.44 +/- 1.0) > sum of CIBz (2.42 +/- 0.18), although these rankings varied considerably over the summer. The alpha- and gamma-HCH and lower chlorinated PCB congeners were the most common POPs in C. hyperboreus. The relationship between bioconcentration factor (BCF) and octanol-water partition coefficient (Kow) observed for the C. hyperboreus was linear and near 1:1 (slope = 0.72) for POPs with a log Kow between 3 and 6 but curvilinear when hydrophobic POPs (log Kow > 6) were included. Concentrations of sum of HCH. Sum of CHLOR and sum of CIBz increased over the sampling period, but no change in sum of PCB or sum of DDT was observed. After removing the effects of time, the variables lipid content, water content, delta15N and delta13C did not describe POP concentrations in C. hyperboreus. These results suggest that hydrophobic POP (log Kow = 3.86.0) concentrations in zooplankton are likely to reflect water concentrations and that POPs do not biomagnify in C. hyperboreus or likely in other small, herbivorous zooplankton.

Determination of the distribution coefficient (log Kd) of oxytetracycline, tylosin A, olaquindox and metronidazole in manure.

PubMed

Loke, Marie-Louise; Tjørnelund, Jette; Halling-Sørensen, Bent

2002-07-01

Olaquindox (log Kow = -2.3) and metronidazole (log Kow = -0.1) both have low tendencies to sorp to particles in manure. This corresponds with the negative log Kow values of these antibiotics. Tylosin (log Kow = 1.63) and oxytetracycline (log Kow = -1.12) sorp relatively strongly to the manure particles and have log Kd values between 1.5 and 2.0. The tendency to bind to manure was ranked after increasing binding as follows: metronidazole < olaquindox < tylosin A and oxytetracycline. This order of ranking is consistent with results of sorption in soil. Our experiments illustrate that for some antibacterial agents estimation of the partitioning coefficients, Kd, cannot be made from Kow and f(oc) alone. Sorption of oxytetracycline to manure is much higher than expected from the negative log Kow value of the compound. It is believed that sorption of oxytetracycline to manure is influenced by ionic binding to divalent metal ions as such Mg2+ and Ca2+ as well as other charged compounds in the matrix. Binding of oxytetracycline to soil is stronger than the binding to manure. This is most likely due to the strong mineral related metal complexes formed between soil, metal ion and oxytetracycline. These complexes are not known to exist in manure. The relatively strong sorption of tylosin A to manure corresponds with data found for soil sorption of tylosin. Tylosin has a log Kow value of 2.5, thus it is not surprising that this drug binds strongly to manure.

Characterization of five passive sampling devices for monitoring of pesticides in water.

PubMed

Ahrens, Lutz; Daneshvar, Atlasi; Lau, Anna E; Kreuger, Jenny

2015-07-31

Five different passive sampler devices were characterized under laboratory conditions for measurement of 124 legacy and current used pesticides in water. In addition, passive sampler derived time-weighted average (TWA) concentrations were compared to time-integrated active sampling in the field. Sampling rates (RS) and passive sampler-water partition coefficients (KPW) were calculated for individual pesticides using silicone rubber (SR), polar organic chemical integrative sampler (POCIS)-A, POCIS-B, Chemcatcher(®) SDB-RPS and Chemcatcher(®) C18. The median RS (Lday(-1)) decreased as follows: SR (0.86)>POCIS-B (0.22)>POCIS-A (0.18)>Chemcatcher(®) SDB-RPS (0.05)>Chemcatcher(®) C18 (0.02), while the median logKPW (Lkg(-1)) decreased as follows: POCIS-B (4.78)>POCIS-A (4.56)>Chemcatcher(®) SDB-RPS (3.17)>SR (3.14)>Chemcatcher(®)C18 (2.71). The uptake of the selected compounds depended on their physicochemical properties, i.e. SR showed a better uptake for more hydrophobic compounds (log octanol-water partition coefficient (KOW)>5.3), whereas POCIS-A, POCIS-B and Chemcatcher(®) SDB-RPS were more suitable for hydrophilic compounds (logKOW<0.70). Overall, the comparison between passive sampler and time-integrated active sampler concentrations showed a good agreement and the tested passive samplers were suitable for capturing compounds with a wide range of KOW's in water. Copyright © 2015 Elsevier B.V. All rights reserved.

Adsorption of pharmaceuticals onto trimethylsilylated mesoporous SBA-15.

PubMed

Bui, Tung Xuan; Pham, Viet Hung; Le, Son Thanh; Choi, Heechul

2013-06-15

The adsorption of a complex mixture of 12 selected pharmaceuticals to trimethylsilylated mesoporous SBA-15 (TMS-SBA-15) has been investigated by batch adsorption experiments. The adsorption of pharmaceuticals to TMS-SBA-15 was highly dependent on the solution pH and pharmaceutical properties (i.e., hydrophobicity (logKow) and acidity (pKa)). Good log-log linear relationships between the adsorption (Kd) and pH-dependent octanol-water coefficients (Kow(pH)) were then established among the neutral, anionic, and cationic compounds, suggesting hydrophobic interaction as a primary driving force in the adsorption. In addition, the neutral species of each compound accounted for a major contribution to the overall compound adsorption onto TMS-SBA-15. The adsorption kinetics of pharmaceuticals was evaluated by the nonlinear first-order and pseudo-second-order models. The first-order model gave a better fit for five pharmaceuticals with lower adsorption capacity, whereas the pseudo-second-order model fitted better for seven pharmaceuticals having higher adsorption capacity. In the same group of properties, pharmaceuticals having higher adsorption capacity exhibited faster adsorption rates. The rate-limiting steps for adsorption of pharmaceuticals onto TMS-SBA-15 are boundary layer diffusion and intraparticle diffusion including diffusion in mesopores and micropores. In addition, the adsorption of pharmaceuticals to TMS-SBA-15 was not influenced by the change of initial pharmaceutical concentration (10-100μgL(-1)) and the presence of natural organic matter. Copyright © 2013 Elsevier B.V. All rights reserved.

Impact of temperature, pH, and salinity changes on the physico-chemical properties of model naphthenic acids.

PubMed

Celsie, Alena; Parnis, J Mark; Mackay, Donald

2016-03-01

The effects of temperature, pH, and salinity change on naphthenic acids (NAs) present in oil-sands process wastewater were modeled for 55 representative NAs. COSMO-RS was used to estimate octanol-water (KOW) and octanol-air (KOA) partition ratios and Henry's law constants (H). Validation with experimental carboxylic acid data yielded log KOW and log H RMS errors of 0.45 and 0.55 respectively. Calculations of log KOW, (or log D, for pH-dependence), log KOA and log H (or log HD, for pH-dependence) were made for model NAs between -20 °C and 40 °C, pH between 0 and 14, and salinity between 0 and 3 g NaCl L(-1). Temperature increase by 60 °C resulted in 3-5 log unit increase in H and a similar magnitude decrease in KOA. pH increase above the NA pKa resulted in a dramatic decrease in both log D and log HD. Salinity increase over the 0-3 g NaCl L(-1) range resulted in a 0.3 log unit increase on average for KOW and H values. Log KOW values of the sodium salt and anion of the conjugate base were also estimated to examine their potential for contribution to the overall partitioning of NAs. Sodium salts and anions of naphthenic acids are predicted to have on average 4 log units and 6 log units lower log KOW values, respectively, with respect to the corresponding neutral NA. Partitioning properties are profoundly influenced by the by the relative prevailing pH and the substance's pKa at the relevant temperature. Copyright © 2015 Elsevier Ltd. All rights reserved.

Impact of particle size on distribution and human exposure of flame retardants in indoor dust.

PubMed

He, Rui-Wen; Li, Yun-Zi; Xiang, Ping; Li, Chao; Cui, Xin-Yi; Ma, Lena Q

2018-04-01

The effect of dust particle size on the distribution and bioaccessibility of flame retardants (FRs) in indoor dust remains unclear. In this study, we analyzed 20 FRs (including 6 organophosphate flame retardants (OPFRs), 8 polybrominated diphenyl ethers (PBDEs), 4 novel brominated flame retardants (NBFRs), and 2 dechlorane plus (DPs)) in composite dust samples from offices, public microenvironments (PME), and cars in Nanjing, China. Each composite sample (one per microenvironment) was separated into 6 size fractions (F1-F6: 200-2000µm, 150-200µm, 100-150µm, 63-100µm, 43-63µm, and <43µm). FRs concentrations were the highest in car dust, being 16 and 6 times higher than those in offices and PME. The distribution of FRs in different size fractions was Kow-dependent and affected by surface area (Log Kow=1-4), total organic carbon (Log Kow=4-9), and FR migration pathways into dust (Log Kow>9). Bioaccessibility of FRs was measured by the physiologically-based extraction test, with OPFR bioaccessibility being 1.8-82% while bioaccessible PBDEs, NBFRs, and DPs were under detection limits due to their high hydrophobicity. The OPFR bioaccessibility in 200-2000µm fraction was significantly higher than that of <43µm fraction, but with no difference among the other four fractions. Risk assessment was performed for the most abundant OPFR-tris(2-chloroethyl) phosphate. The average daily dose (ADD) values were the highest for the <43µm fraction for all three types of dust using total concentrations, but no consistent trend was found among the three types of dust if based on bioaccessible concentrations. Our results indicated that dust size impacted human exposure estimation of FRs due to their variability in distribution and bioaccessibility among different fractions. For future risk assessment, size selection for dust sampling should be standardized and bioaccessibility of FRs should not be overlooked. Copyright © 2018 Elsevier Inc. All rights reserved.

Effects of chain length, chlorination degree, and structure on the octanol-water partition coefficients of polychlorinated n-alkanes.

PubMed

Hilger, Bettina; Fromme, Hermann; Völkel, Wolfgang; Coelhan, Mehmet

2011-04-01

Log octanol-water partition coefficients (log Kow) of 40 synthesized polychlorinated n-alkanes (PCAs) with different chlorination degrees were determined using reversed-phase high performance liquid chromatography (RP-HPLC). In addition, log Kow values of a technical mixture namely Cereclor 63L as well as 15 individual in house synthesized C10, C11, and C12 chloroalkanes with known chlorine positions were estimated. Based on these results, the effects of chain length, chlorination degree, and structure were explored. The estimated log Kow values ranged from 4.10 (polychlorinated n-decanes with 50.2% chlorine content) to 11.34 (polychlorinated n-octacosanes with 54.8% chlorine content) for PCAs and from 3.82 (1,2,5,6,9,10-hexachlorodecane) to 7.75 (1,1,1,3,9,11,11,11-octachlorododecane) for the individual chloroalkanes studied. The results showed that log Kow value was influenced linearly at a given chlorine content by chain length, while a polynominal effect was observed in dependence on the chlorination degree of an alkane chain. Chlorine substitution pattern influenced markedly the log Kow value of chloroalkanes.

Estimation of octanol/water partition coefficients using LSER parameters

USGS Publications Warehouse

Luehrs, Dean C.; Hickey, James P.; Godbole, Kalpana A.; Rogers, Tony N.

1998-01-01

The logarithms of octanol/water partition coefficients, logKow, were regressed against the linear solvation energy relationship (LSER) parameters for a training set of 981 diverse organic chemicals. The standard deviation for logKow was 0.49. The regression equation was then used to estimate logKow for a test of 146 chemicals which included pesticides and other diverse polyfunctional compounds. Thus the octanol/water partition coefficient may be estimated by LSER parameters without elaborate software but only moderate accuracy should be expected.

Predictive performance of the human Cell Line Activation Test (h-CLAT) for lipophilic chemicals with high octanol-water partition coefficients.

PubMed

Takenouchi, Osamu; Miyazawa, Masaaki; Saito, Kazutoshi; Ashikaga, Takao; Sakaguchi, Hitoshi

2013-01-01

To meet the urgent need for a reliable alternative test for predicting skin sensitizing potential of many chemicals, we have developed a cell-based in vitro test, human Cell Line Activation Test (h-CLAT). However, the predictive performance for lipophilic chemicals in the h-CLAT still remains relatively unknown. Moreover, it's suggested that low water solubility of chemicals might induce false negative outcomes. Thus, in this study, we tested relatively low water soluble 37 chemicals with log Kow values above and below 3.5 in the h-CLAT. The small-scale assessment resulted in nine false negative outcomes for chemicals with log Kow values greater than 3.5. We then created a dataset of 143 chemicals by combining the existing dataset of 106 chemicals and examined the predictive performance of the h-CLAT for chemicals with a log Kow of less than 3.5; a total of 112 chemicals from the 143 chemicals in the dataset. The sensitivity and overall accuracy for the 143 chemicals were 83% and 80%, respectively. In contrast, sensitivity and overall accuracy for the 112 chemicals with log Kow values below 3.5 improved to 94% and 88%, respectively. These data suggested that the h-CLAT could successfully detect sensitizers with log Kow values up to 3.5. When chemicals with log Kow values greater than 3.5 that were deemed positive by h-CLAT were included with the 112 chemicals, the sensitivity and accuracy in terms of the resulting applicable 128 chemicals out of the 143 chemicals became 95% and 88%, respectively. The use of log Kow values gave the h-CLAT a higher predictive performance. Our results demonstrated that the h-CLAT could predict sensitizing potential of various chemicals, which contain lipophilic chemicals using a large-scale chemical dataset.

Bioconcentration of chlorinated hydrocarbons from sediment by oligochaetes

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

Connell, D.W.; Bowman, M.; Hawker, D.W.

1988-12-01

Previously published data on the accumulation of 15 chlorinated hydrocarbons from sediment by oligochaetes have been interpreted on the basis of bioconcentration from interstitial water. Calculation of the interstitial water concentration allowed determination of uptake and clearance rate constants together with bioconcentration factors (KB) for these compounds. These three factors each exhibited a systematic relationship to the octanol/water partition coefficient (KOW). The log KB versus log KOW relationship was roughly linear over the log KOW range from 4.4 to 6.4 and displayed an increasing nonlinear deviation for log KOW values greater than 6.4. These relationships are qualitatively similar to thosemore » established for other aquatic organisms where bioconcentration from water was the mechanism involved. This suggests that interstitial water may be the phase from which lipophilic compounds in sediment are bioconcentrated by oligochaetes. An expression relating the bioconcentration factor to the biotic concentration and various sediment characteristics has also been developed.« less

Comparison of Toxicities to Vibrio fischeri and Fish Based on Discrimination of Excess Toxicity from Baseline Level

PubMed Central

Wang, Xiao H.; Yu, Yang; Huang, Tao; Qin, Wei C.; Su, Li M.; Zhao, Yuan H.

2016-01-01

Investigations on the relationship of toxicities between species play an important role in the understanding of toxic mechanisms to environmental organisms. In this paper, the toxicity data of 949 chemicals to fish and 1470 chemicals to V. fischeri were used to investigate the modes of action (MOAs) between species. The results show that although there is a positive interspecies correlation, the relationship is poor. Analysis on the excess toxicity calculated from toxic ratios (TR) shows that many chemicals have close toxicities and share the same MOAs between the two species. Linear relationships between the toxicities and octanol/water partition coefficient (log KOW) for baseline and less inert compounds indicate that the internal critical concentrations (CBRs) approach a constant both to fish and V. fischeri for neutral hydrophobic compounds. These compounds share the same toxic mechanisms and bio-uptake processes between species. On the other hand, some hydrophilic compounds exhibit different toxic effects with greatly different log TR values between V. fischeri and fish species. These hydrophilic compounds were identified as reactive MOAs to V. fischeri, but not to fish. The interspecies correlation is improved by adding a hydrophobic descriptor into the correlation equation. This indicates that the differences in the toxic ratios between fish and V. fischeri for these hydrophilic compounds can be partly attributed to the differences of bioconcentration between the two species, rather than the differences of reactivity with the target macromolecules. These hydrophilic compounds may more easily pass through the cell membrane of V. fischeri than the gill and skin of fish, react with the target macromolecules and exhibit excess toxicity. The compounds with log KOW > 7 exhibiting very low toxicity (log TR < –1) to both species indicate that the bioconcentration potential of a chemical plays a very important role in the identification of excess toxicity and MOAs. PMID:26901437

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).

Variation in bioaccumulation of persistent organic pollutants based on octanol-air partitioning: Influence of respiratory elimination in marine species.

PubMed

Moses, Sara K; Harley, John R; Lieske, Camilla L; Muir, Derek C G; Whiting, Alex V; O'Hara, Todd M

2015-11-15

Risk assessments of persistent organic pollutants (POPs) are often based on octanol-water (KOW) partitioning dynamics and may not adequately reflect bioaccumulation in air-breathing organisms. It has been suggested that compounds with low KOW and high octanol-air partitioning (KOA) coefficients have the potential to bioaccumulate in air-breathing organisms, including marine mammals. Here we evaluate differences in concentrations of POPs for two trophically matched Arctic species, spotted seal (Phoca largha) and sheefish (Stenodus leucichthys). We compared concentrations of 108 POPs in matched tissues (liver and muscle) across three ranges of KOW. We found a significant positive correlation between POP concentration and log KOA in spotted seal tissues for low log KOW compounds (log KOW <5.5, p<0.05). This provides further evidence for empirical models and observed bioaccumulation patterns in air-breathing organisms, and highlights the potential for bioaccumulation of these compounds in Arctic marine mammals. Copyright © 2015 Elsevier Ltd. All rights reserved.

Variation in bioaccumulation of persistent organic pollutants based on octanol-air partitioning: Influence of respiratory elimination in marine species

PubMed Central

Moses, Sara K.; Harley, John R.; Lieske, Camilla L.; Muir, Derek C.G.; Whiting, Alex V.; O'Hara, Todd M.

2015-01-01

Risk assessments of persistent organic pollutants (POPs) are often based on octanol-water (KOW) partitioning dynamics and may not adequately reflect bioaccumulation in air-breathing organisms. It has been suggested that compounds with low KOW and high octanol-air partitioning (KOA) coefficients have the potential to bioaccumulate in air-breathing organisms, including marine mammals. Here we evaluate differences in concentrations of POPs for two trophically matched Arctic species, spotted seal (Phoca largha) and sheefish (Stenodus leucichthys). We compared concentrations of 108 POPs in matched tissues (liver and muscle) across three ranges of KOW. We found a significant positive correlation between POP concentration and log KOA in spotted seal tissues for low log KOW compounds (log KOW <5.5, p<0.05). This provides further evidence for empirical models and observed bioaccumulation patterns in air-breathing organisms, and highlights the potential for bioaccumulation of these compounds in Arctic marine mammals. PMID:26440545

A biomimetic approach to the detection and identification of estrogen receptor agonists in surface waters using semipermeable membrane devices (SPMDs) and bioassay-directed chemical analysis.

PubMed

Rastall, Andrew C; Getting, Dominic; Goddard, Jon; Roberts, David R; Erdinger, Lothar

2006-07-01

Some anthropogenic pollutants posses the capacity to disrupt endogenous control of developmental and reproductive processes in aquatic biota by activating estrogen receptors. Many anthropogenic estrogen receptor agonists (ERAs) are hydrophobic and will therefore readily partition into the abiotic organic carbon phases present in natural waters. This partitioning process effectively reduces the proportion of ERAs readily available for bioconcentration by aquatic biota. Results from some studies have suggested that for many aquatic species, bioconcentration of the freely-dissolved fraction may be the principal route of uptake for hydrophobic pollutants with logarithm n-octanol/water partition coefficient (log Kow) values less than approximately 6.0, which includes the majority of known anthropogenic ERAs. The detection and identification of freely-dissolved readily bioconcentratable ERAs is therefore an important aspect of exposure and risk assessment. However, most studies use conventional techniques to sample total ERA concentrations and in doing so frequently fail to account for bioconcentration of the freely-dissolved fraction. The aim of the current study was to couple the biomimetic sampling properties of semipermeable membrane devices (SPMDs) to a bioassay-directed chemical analysis (BDCA) scheme for the detection and identification of readily bioconcentratable ERAs in surface waters. SPMDs were constructed and deployed at a number of sites in Germany and the UK. Following the dialytic recovery of target compounds and size exclusion chromatographic cleanup, SPMD samples were fractionated using a reverse-phase HPLC method calibrated to provide an estimation of target analyte log Kow. A portion of each HPLC fraction was then subjected to the yeast estrogen screen (YES) to determine estrogenic potential. Results were plotted in the form of 'estrograms' which displayed profiles of estrogenic potential as a function of HPLC retention time (i.e. hydrophobicity) for each of the samples. Where significant activity was elicited in the YES, the remaining portion of the respective active fraction was subjected to GC-MS analysis in an attempt to identify the ERAs present. Estrograms from each of the field samples showed that readily bioconcentratable ERAs were present at each of the sampling sites. Estimated log Kow values for the various active fractions ranged from 1.92 to 8.63. For some samples, estrogenic potential was associated with a relatively narrow range of log Kow values whilst in others estrogenic potential was more widely distributed across the respective estrograms. ERAs identified in active fractions included some benzophenones, various nonylphenol isomers, benzyl butyl phthalate, dehydroabietic acid, sitosterol, 3-(4-methylbenzylidine)camphor (4-MBC) and 6-acetyl-1,1,2,4,4,7-hexamethyltetralin (AHTN). Other tentatively identified compounds which may have contributed to the observed YES activity included various polycyclic aromatic hydrocarbons (PAHs) and their alkylated derivatives, methylated benzylphenols, various alkyl-phenols and dialkylphenols. However, potential ERAs present in some active fractions remain unidentified. Our results show that SPMD-YES-based BDCA can be used to detect and identify readily bioconcentratable ERAs in surface waters. As such, this biomimetic approach can be employed as an alternative to conventional methodologies to provide investigators with a more environmentally relevant insight into the distribution and identity of ERAs in surface waters. The use of alternative bioassays also has the potential to expand SPMD-based BDCA to include a wide range of toxicological endpoints. Improvements to the analytical methodology used to identify ERAs or other target compounds in active fractions in the current study could greatly enhance the applicability of the methodology to risk assessment and monitoring programmes.

Improved prediction of octanol-water partition coefficients from liquid-solute water solubilities and molar volumes

USGS Publications Warehouse

Chiou, C.T.; Schmedding, D.W.; Manes, M.

2005-01-01

A volume-fraction-based solvent-water partition model for dilute solutes, in which the partition coefficient shows a dependence on solute molar volume (V??), is adapted to predict the octanol-water partition coefficient (K ow) from the liquid or supercooled-liquid solute water solubility (Sw), or vice versa. The established correlation is tested for a wide range of industrial compounds and pesticides (e.g., halogenated aliphatic hydrocarbons, alkylbenzenes, halogenated benzenes, ethers, esters, PAHs, PCBs, organochlorines, organophosphates, carbamates, and amidesureas-triazines), which comprise a total of 215 test compounds spanning about 10 orders of magnitude in Sw and 8.5 orders of magnitude in Kow. Except for phenols and alcohols, which require special considerations of the Kow data, the correlation predicts the Kow within 0.1 log units for most compounds, much independent of the compound type or the magnitude in K ow. With reliable Sw and V data for compounds of interest, the correlation provides an effective means for either predicting the unavailable log Kow values or verifying the reliability of the reported log Kow data. ?? 2005 American Chemical Society.

From Clothing to Laundry Water: Investigating the Fate of Phthalates, Brominated Flame Retardants, and Organophosphate Esters.

PubMed

Saini, Amandeep; Thaysen, Clara; Jantunen, Liisa; McQueen, Rachel H; Diamond, Miriam L

2016-09-06

The accumulation of phthalate esters, brominated flame retardants (BFRs) and organophosphate esters (OPEs) by clothing from indoor air and transfer via laundering to outdoors were investigated. Over 30 days cotton and polyester fabrics accumulated 3475 and 1950 ng/dm(2) ∑5phthalates, 65 and 78 ng/dm(2) ∑10BFRs, and 1200 and 310 ng/dm(2) ∑8OPEs, respectively. Planar surface area concentrations of OPEs and low molecular weight phthalates were significantly greater in cotton than polyester and similar for BFRs and high molecular weight phthalates. This difference was significantly and inversely correlated with KOW, suggesting greater sorption of polar compounds to polar cotton. Chemical release from cotton and polyester to laundry water was >80% of aliphatic OPEs (log KOW < 4), < 50% of OPEs with an aromatic structure, 50-100% of low molecular weight phthalates (log KOW 4-6), and < detection-35% of higher molecular weight phthalates (log KOW > 8) and BFRs (log KOW > 6). These results support the hypothesis that clothing acts an efficient conveyer of soluble semivolatile organic compounds (SVOCs) from indoors to outdoors through accumulation from air and then release during laundering. Clothes drying could as well contribute to the release of chemicals emitted by electric dryers. The results also have implications for dermal exposure.

Three-compartment model for contaminant accumulation by semipermeable membrane devices

USGS Publications Warehouse

Gale, Robert W.

1998-01-01

Passive sampling of dissolved hydrophobic contaminants with lipid (triolein)-containing semipermeable membrane devices (SPMDs) has been gaining acceptance for environmental monitoring. Understanding of the accumulation process has employed a simple polymer film-control model of uptake by the polymer-enclosed lipid, while aqueous film control has been only briefly discussed. A more complete three-compartment model incorporating both aqueous film (turbulent-diffusive) and polymer film (diffusive) mass transfer is developed here and is fit to data from accumulation studies conducted in constant-concentration, flow-through dilutors. This model predicts aqueous film control of the whole device for moderate to high Kow compounds, rather than polymer film control. Uptake rates for phenanthrene and 2,2‘,5,5‘-tetrachlorobiphenyl were about 4.8 and 4.2 L/day/standard SPMD, respectively. Maximum 28 day SPMD concentration factors of 30 000 are predicted for solutes with log Kow values of >5.5. Effects of varying aqueous and polymer film thicknesses and solute diffusivities in the polymer film are modeled, and overall accumulation by the whole device is predicted to remain under aqueous film control, although accumulation in the triolein may be subject to polymer film control. The predicted half-life and integrative response of SPMDs to pulsed concentration events is proportional to log KSPMD.

Experimental Solubility Approach to Determine PDMS-Water Partition Constants and PDMS Activity Coefficients.

PubMed

Grant, Sharon; Schacht, Veronika J; Escher, Beate I; Hawker, Darryl W; Gaus, Caroline

2016-03-15

Freely dissolved aqueous concentration and chemical activity are important determinants of contaminant transport, fate, and toxic potential. Both parameters are commonly quantified using Solid Phase Micro-Extraction (SPME) based on a sorptive polymer such as polydimethylsiloxane (PDMS). This method requires the PDMS-water partition constants, KPDMSw, or activity coefficient to be known. For superhydrophobic contaminants (log KOW >6), application of existing methods to measure these parameters is challenging, and independent measures to validate KPDMSw values would be beneficial. We developed a simple, rapid method to directly measure PDMS solubilities of solid contaminants, SPDMS(S), which together with literature thermodynamic properties was then used to estimate KPDMSw and activity coefficients in PDMS. PDMS solubility for the test compounds (log KOW 7.2-8.3) ranged over 3 orders of magnitude (4.1-5700 μM), and was dependent on compound class. For polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins (PCDDs), solubility-derived KPDMSw increased linearly with hydrophobicity, consistent with trends previously reported for less chlorinated congeners. In contrast, subcooled liquid PDMS solubilities, SPDMS(L), were approximately constant within a compound class. SPDMS(S) and KPDMSw can therefore be predicted for a compound class with reasonable robustness based solely on the class-specific SPDMS(L) and a particular congener's entropy of fusion, melting point, and aqueous solubility.

Uptake and depuration of nonionic organic contaminants from sediment by the oligochaete, Lumbriculus variegatus

USGS Publications Warehouse

Ingersoll, Christopher G.; Brunson, Eric L.; Wang, Ning; Dwyer, James F.; Ankley, Gerald T.; Mount, David R.; Huckins, James; Petty, J.; Landrum, Peter F.

2003-01-01

Uptake of sediment-associated contaminants by the oligochaete Lumbriculus variegatus was evaluated after 1, 3, 7, 14, 28, and 56 d of exposure to a field-collected sediment contaminated with DDT and its metabolites, dichlorodiphenyldichloroethane (DDD) and dichlorodiphenyldichloroethylene (DDE), or to a field-collected sediment contaminated with polycyclic aromatic hydrocarbons (PAHs). Depuration of contaminants by oligochaetes in a control sediment or in water was also evaluated over a 7-d period after 28 d of exposure to the field-collected sediments. Accumulation of PAHs with a log octanol-water partitioning coefficient (log Kow) 5.6 or DDD and DDE typically exhibited a steady increase from day 1 to about day 14 or 28, followed by a plateau. Therefore, exposures conducted for a minimum of 14 to 28 d better reflected steady-state concentrations for DDT and its metabolites and for PAHs. Depuration rates for DDT and its metabolites and high-Kow PAHs were much higher in organisms held in clean sediment relative to both water-only depuration and model predictions. This suggests that depuration in clean sediment may artificially accelerate depuration of hydrophobic compounds. Comparisons between laboratory-exposed L. variegatus and oligochaetes collected in the field from these sediments indicate that results of laboratory tests can be extrapolated to the field with a reasonable degree of certainty.

Sorption capacity of plastic debris for hydrophobic organic chemicals.

PubMed

Lee, Hwang; Shim, Won Joon; Kwon, Jung-Hwan

2014-02-01

The occurrence of microplastics (MPs) in the ocean is an emerging world-wide concern. Due to high sorption capacity of plastics for hydrophobic organic chemicals (HOCs), sorption may play an important role in the transport processes of HOCs. However, sorption capacity of various plastic materials is rarely documented except in the case of those used for environmental sampling purposes. In this study, we measured partition coefficients between MPs and seawater (KMPsw) for 8 polycyclic aromatic hydrocarbons (PAHs), 4 hexachlorocyclohexanes (HCHs) and 2 chlorinated benzenes (CBs). Three surrogate polymers - polyethylene, polypropylene, and polystyrene - were used as model plastic debris because they are the major components of microplastic debris found. Due to the limited solubility of HOCs in seawater and their long equilibration time, a third-phase partitioning method was used for the determination of KMPsw. First, partition coefficients between polydimethylsiloxane (PDMS) and seawater (KPDMSsw) were measured. For the determination of KMPsw, the distribution of HOCs between PDMS or plastics and solvent mixture (methanol:water=8:2 (v/v)) was determined after apparent equilibrium up to 12 weeks. Plastic debris was prepared in a laboratory by physical crushing; the median longest dimension was 320-440 μm. Partition coefficients between polyethylene and seawater obtained using the third-phase equilibrium method agreed well with experimental partition coefficients between low-density polyethylene and water in the literature. The values of KMPsw were generally in the order of polystyrene, polyethylene, and polypropylene for most of the chemicals tested. The ranges of log KMPsw were 2.04-7.87, 2.18-7.00, and 2.63-7.52 for polyethylene, polypropylene, and polystyrene, respectively. The partition coefficients of plastic debris can be as high as other frequently used partition coefficients, such as 1-octanol-water partition coefficients (Kow) and log KMPsw showed good linear correlations with log Kow. High sorption capacity of microplastics implies the importance of MP-associated transport of HOCs in the marine environment. © 2013 Elsevier B.V. All rights reserved.

Sorption of structurally different ionized pharmaceutical and illicit drugs to a mixed-mode coated microsampler.

PubMed

Peltenburg, Hester; Timmer, Niels; Bosman, Ingrid J; Hermens, Joop L M; Droge, Steven T J

2016-05-20

The mixed-mode (C18/strong cation exchange-SCX) solid-phase microextraction (SPME) fiber has recently been shown to have increased sensitivity for ionic compounds compared to more conventional sampler coatings such as polyacrylate and polydimethylsiloxane (PDMS). However, data for structurally diverse compounds to this (prototype) sampler coating are too limited to define its structural limitations. We determined C18/SCX fiber partitioning coefficients of nineteen cationic structures without hydrogen bonding capacity besides the charged group, stretching over a wide hydrophobicity range (including amphetamine, amitriptyline, promazine, chlorpromazine, triflupromazine, difenzoquat), and eight basic pharmaceutical and illicit drugs (pKa>8.86) with additional hydrogen bonding moieties (MDMA, atenolol, alprenolol, metoprolol, morphine, nicotine, tramadol, verapamil). In addition, sorption data for three neutral benzodiazepines (diazepam, temazepam, and oxazepam) and the anionic NSAID diclofenac were collected to determine the efficiency to sample non-basic drugs. All tested compounds showed nonlinear isotherms above 1mmol/L coating, and linear isotherms below 1mmol/L. The affinity for C18/SCX-SPME for tested organic cations without Hbond capacities increased with longer alkyl chains, ranging from logarithmic fiber-water distribution coefficients (log Dfw) of 1.8 (benzylamine) to 5.8 (triflupromazine). Amines smaller than benzylamine may thus have limited detection levels, while cationic surfactants with alkyl chain lengths >12 carbon atoms may sorb too strong to the C18/SCX sampler which hampers calibration of the fiber-water relationship in the linear range. The log Dfw for these simple cation structures closely correlates with the octanol-water partition coefficient of the neutral form (Kow,N), and decreases with increased branching and presence of multiple aromatic rings. Oxygen moieties in organic cations decreased the affinity for C18/SCX-SPME. Log Dfw values of neutral benzodiazepines were an order of magnitude higher than their log Kow,N. Results for anionic diclofenac species (logKow,N 4.5, pKa 4.0, log Dfw 2.9) indicate that the C18-SCX fiber might also be useful for sampling of organic anions. This data supports our theory that C18-based coatings are able to sorb ionized compounds through adsorption and demonstrates the applicability of C18-based SPME in the measurement of freely dissolved concentrations of a wide range of ionizable compounds. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Is skin penetration a determining factor in skin sensitization potential and potency? Refuting the notion of a LogKow threshold for Skin Sensitization

EPA Science Inventory

Summary:Background. It is widely accepted that substances that cannot penetrate through the skin will not be sensitisers. Thresholds based on relevant physicochemical parameters such as a LogKow > 1 and a MW < 500, are assumed and widely accepted as self-evident truths. Objective...

Rapid determination of octanol-water partition coefficient using vortex-assisted liquid-liquid microextraction.

PubMed

Román, Iván P; Mastromichali, Anna; Tyrovola, Konstantina; Canals, Antonio; Psillakis, Elefteria

2014-02-21

Vortex-assisted liquid-liquid microextraction (VALLME) coupled with high-performance liquid chromatography (HPLC) is proposed here for the rapid determination of octanol-water partitioning coefficients (Kow). VALLME uses vortex agitation, a mild emulsification procedure, to disperse microvolumes of octanol in the aqueous phase thus increasing the interfacial contact area and ensuring faster partitioning rates. With VALLME, 2min were enough to achieve equilibrium conditions between the octanolic and aqueous phases. Upon equilibration, separation was achieved using centrifugation and the octanolic microdrop was collected and analyzed in a HPLC system. Six model compounds with logKow values ranging between ∼0.5 and 3.5 were used during the present investigations. The proposed method produced logKow values that were consistent with previously published values and the recorded uncertainty was well within the acceptable log unit range. Overall, the key features of the proposed Kow determination procedure comprised speed, reliability, simplicity, low cost and minimal solvent consumption. Copyright © 2014 Elsevier B.V. All rights reserved.

A new concept for the environmental risk assessment of poorly water soluble compounds and its application to consumer products.

PubMed

Tolls, Johannes; Müller, Martin; Willing, Andreas; Steber, Josef

2009-07-01

Many consumer products contain lipophilic, poorly soluble ingredients representing large-volume substances whose aquatic toxicity cannot be adequately determined with standard methods for a number of reasons. In such cases, a recently developed approach can be used to define an aquatic exposure threshold of no concern (ETNCaq; i.e., a concentration below which no adverse affects on the environment are to be expected). A risk assessment can be performed by comparing the ETNCaq value with the aquatic exposure levels of poorly soluble substances. Accordingly, the aquatic exposure levels of substances with water solubility below the ETNCaq will not exceed the ecotoxicological no-effect concentration; therefore, their risk can be assessed as being negligible. The ETNCaq value relevant for substances with a narcotic mode of action is 1.9 microg/L. To apply the above risk assessment strategy, the solubility in water needs to be known. Most frequently, this parameter is estimated by means of quantitative structure/activity relationships based on the log octanol-water partition coefficient (log Kow). The predictive value of several calculation models for water solubility has been investigated by this method with the use of more recent experimental solubility data for lipophilic compounds. A linear regression model was shown to be the most suitable for providing correct predictions without underestimation of real water solubility. To define a log Kow threshold suitable for reliably predicting a water solubility of less than 1.9 microg/L, a confidence limit was established by statistical comparison of the experimental solubility data with their log Kow. It was found that a threshold of log Kow = 7 generally allows discrimination between substances with solubility greater than and less than 1.9 microg/L. Accordingly, organic substances with a baseline toxicity and log Kow > 7 do not require further testing to prove that they have low environmental risk. In applying this concept, the uncertainty of the prediction of water solubility can be accounted for. If the predicted solubility in water is to be below ETNCaq with a probability of 95%, the corresponding log Kow value is 8.

Bioaccumulation and translocation of polyhalogenated compounds in rice (Oryza sativa L.) planted in paddy soil collected from an electronic waste recycling site, South China.

PubMed

Zhang, Yun; Luo, Xiao-Jun; Mo, Ling; Wu, Jiang-Ping; Mai, Bi-Xian; Peng, Yong-Hong

2015-10-01

The bioaccumulation and translocation of polyhalogenated compounds (PHCs) in rice planted in the paddy soils of an electronic waste (e-waste) recycling site were investigated, along with the effect of contaminated soils on rice growth. The PHCs included polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), decabromodiphenyl ethane (DBDPE), 1,2-bis(2,4,6-tribromophenoxy) ethane (BTBPE), and dechlorane plus (DPs). The morphological development and all measured physiological parameters of rice plants except for peroxidase were significantly inhibited by e-waste contaminated soils. Specifically, soil-root bioaccumulation factors (RCFs) increased with increasing logarithm of octanol-water partition coefficient (logKow) for PCBs, but decreased for PBDEs. During translocation from root to stem, translocation factors (TFs) and logKow were positively correlated. However, the accumulation mechanism in the leaf was concentration-dependent. In the high concentration exposure group, translocation play more important role in determination PHCs burden in leaf than atmospheric uptake, with logTF (from stem to leaf) being positively correlated with logKow. In contrast, in the low exposure and control groups, logTF (from stem to leaf) was negatively correlated with logKow. In addition, Syn-DP was selectively accumulated in plant tissues. In conclusion, this study demonstrates that e-waste contaminated soils affect rice growth, revealed the rule of the bioaccumulation and translocation of PHCs in rice plants. Copyright © 2015 Elsevier Ltd. All rights reserved.

QSAR models for predicting octanol/water and organic carbon/water partition coefficients of polychlorinated biphenyls.

PubMed

Yu, S; Gao, S; Gan, Y; Zhang, Y; Ruan, X; Wang, Y; Yang, L; Shi, J

2016-04-01

Quantitative structure-property relationship modelling can be a valuable alternative method to replace or reduce experimental testing. In particular, some endpoints such as octanol-water (KOW) and organic carbon-water (KOC) partition coefficients of polychlorinated biphenyls (PCBs) are easier to predict and various models have been already developed. In this paper, two different methods, which are multiple linear regression based on the descriptors generated using Dragon software and hologram quantitative structure-activity relationships, were employed to predict suspended particulate matter (SPM) derived log KOC and generator column, shake flask and slow stirring method derived log KOW values of 209 PCBs. The predictive ability of the derived models was validated using a test set. The performances of all these models were compared with EPI Suite™ software. The results indicated that the proposed models were robust and satisfactory, and could provide feasible and promising tools for the rapid assessment of the SPM derived log KOC and generator column, shake flask and slow stirring method derived log KOW values of PCBs.

QSPR models for predicting generator-column-derived octanol/water and octanol/air partition coefficients of polychlorinated biphenyls.

PubMed

Yuan, Jintao; Yu, Shuling; Zhang, Ting; Yuan, Xuejie; Cao, Yunyuan; Yu, Xingchen; Yang, Xuan; Yao, Wu

2016-06-01

Octanol/water (K(OW)) and octanol/air (K(OA)) partition coefficients are two important physicochemical properties of organic substances. In current practice, K(OW) and K(OA) values of some polychlorinated biphenyls (PCBs) are measured using generator column method. Quantitative structure-property relationship (QSPR) models can serve as a valuable alternative method of replacing or reducing experimental steps in the determination of K(OW) and K(OA). In this paper, two different methods, i.e., multiple linear regression based on dragon descriptors and hologram quantitative structure-activity relationship, were used to predict generator-column-derived log K(OW) and log K(OA) values of PCBs. The predictive ability of the developed models was validated using a test set, and the performances of all generated models were compared with those of three previously reported models. All results indicated that the proposed models were robust and satisfactory and can thus be used as alternative models for the rapid assessment of the K(OW) and K(OA) of PCBs. Copyright © 2016 Elsevier Inc. All rights reserved.

Does lipophilicity of toxic compounds determine effects on drought tolerance of the soil collembolan Folsomia candida?

PubMed

Skovlund, Gitte; Damgaard, Christian; Bayley, Mark; Holmstrup, Martin

2006-12-01

The ability of Collembola to survive drought stress is crucial for their distribution in the terrestrial environment. Previous studies have suggested that several toxic compounds affect the drought tolerance of Folsomia candida in a synergistic manner and that these compounds have the feature in common that they elicit their toxicity by causing membrane damage. We hypothesised that the detrimental effect of toxic chemicals on drought tolerance in F. candida depends on the lipophilicity (log K(ow)) of the compound because a higher log K(ow) would mean a closer interaction with membranes. In this study the three chemicals 4-nonylphenol, pyrene and p,p'-DDE were tested. Surprisingly, 4-nonylphenol, with the lowest log K(ow), was the most potent with respect to reducing drought tolerance followed by pyrene, suggesting that interactions between drought tolerance and chemical stress do not depend on lipophilicity alone.

Age-related polychlorinated biphenyl dynamics in immature bull sharks (Carcharhinus leucas).

PubMed

Olin, Jill A; Beaudry, Marina; Fisk, Aaron T; Paterson, Gordon

2014-01-01

Polychlorinated biphenyls (PCBs) were quantified in liver tissues of bull sharks (Carcharhinus leucas) ranging in age from <4 wk to >3 yr. Summed values of PCBs (ΣPCBs) ranged from 310 ng/g to 22 070 ng/g (lipid wt) across age classes with ΣPCB concentrations for the youngest sharks in the present study (<4 wk; 5230 ± 2170 ng/g lipid wt) determined to not significantly differ from those quantified in >3-yr-old sharks, highlighting the extent of exposure of this young life stage to this class of persistent organic pollutants (POPs). Age normalization of PCB congener concentrations to those measured for the youngest sharks demonstrated a significant hydrophobicity (log octanol/water partition coefficient [KOW ]) effect that was indicative of maternal offloading of highly hydrophobic (log KOW ≥6.5) congeners to the youngest individuals. A distinct shift in the PCB congener profiles was also observed as these young sharks grew in size. This shift was consistent with a transition from the maternally offloaded signal to the initiation of exogenous feeding and the contributions of mechanisms including growth dilution and whole-body elimination. These results add to the growing pool of literature documenting substantially high concentrations of POPs in juvenile sharks that are most likely attributable to maternal offloading. Collectively, such results underscore the potential vulnerability of young sharks to POP exposure and pose additional concerns for shark-conservation efforts. © 2013 SETAC.

Sorption of benzimidazole anthelmintics to dissolved organic matter surrogates and sewage sludge.

PubMed

Kim, Hyo-Jung; Lee, Dong Soo; Kwon, Jung-Hwan

2010-06-01

The sorption coefficients of four rarely studied zwitterionic pharmaceuticals (benzimidazoles: fenbendazole, albendazole, thiabendazole and flubendazole) and four metabolites of fenbendazole to various dissolved organic matter surrogates (humic acid, sodium dodecyl sulfate micelle, hydroxypropyl-beta-cyclodextrin and liposomes made of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC), and sewage sludge) were measured to extend the available sorption coefficients and eventually to evaluate their environmental fate in soil and water environment. For the entire range of dissolved organic matters, the more hydrophobic fenbendazole and albendazole had higher sorption coefficients than thiabendazole and flubendazole, indicating that the traditional hypothesis of hydrophobic interaction holds for zwitterionic benzimidazole anthelmintics. However, the sorption coefficients of a given benzimidazole to selected dissolved organic matters (DOMs) varied within an order of magnitude. The measured K(oc) values decreased in the order of fenbendazole, albendazole, thiabendazole and flubendazole for sewage sludge and hydroxypropyl-beta-cyclodextrin whereas the orders were different for the other DOM surrogates, implying the hydrophilic nature of sewage sludge. This was also supported by the (N+O)/C elemental ratio of the sewage sludge sample used in this study. The correlations between log K(oc) and log K(ow) were weak (r(2)=0.28-0.64) and the magnitude of the sorption coefficients to the hydrophilic organic matters (hydroxypropyl-beta-cyclodextrin and sewage sludge) were similar to or slightly smaller than those for the hydrophobic organic matters (humic acids and liposome). This suggests that specific hydrophilic interactions also play a significant role in the sorption of moderately hydrophobic benzimidazoles to organic matters. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Estimation of Koc values for deuterated benzene, toluene, and ethylbenzene, and application to ground water contamination studies.

PubMed

Poulson, S R; Drever, J I; Colberg, P J

1997-11-01

Sorption partition coefficients between water and organic carbon (Koc) for deuterated benzene, toluene, and ethylbenzene have been estimated by measuring values of the octanol-water partition coefficient (Kow) and HPLC retention factors (k1), which correlate closely to values of Koc. Measured values of log Kow for non-deuterated and deuterated toluene are 2.77 (+/- 0.02) and 2.78 (+/- 0.04), respectively, indicating that within experimental error, log Koc for deuterated and non-deuterated toluene are the same. The HPLC method provides greater precision, and yields values of delta log Koc (= log Koc [deuterated]-log Koc [non-deuterated]) of -0.021 (+/- 0.001) for benzene, -0.028 (+/- 0.002) for toluene, and -0.035 (+/- 0.003) for ethylbenzene. The small values of delta log Koc demonstrates that deuterated compounds are excellent tracers for the hydrologic behavior of ground water contaminants.

ORD-017311_Data_Brown_DermPerm.xlsx

EPA Pesticide Factsheets

List of chemicals used for model evaluation, their MW, log KOW, and references for the original data source(s), the review(s) the data was collected from, and reference for log KOW as cited in the reviews. [Table SI-3 of research article]This dataset is associated with the following publication:Brown, T., J. Armitage, P. Egeghy, I. Kircanski, and J. Arnot. Dermal permeation data and models for the prioritization and screening-level exposure assessment of organic chemicals. ENVIRONMENT INTERNATIONAL. Elsevier Science Ltd, New York, NY, USA, 94: 424-435, (2016).

OCTANOL/WATER PARTITION COEFFICIENTS AND WATER SOLUBILITIES OF PHTHALATE ESTERS

EPA Science Inventory

Measurements of the octanol/water partition coefficients (K-ow) and water solubilities of di-n-octyl phthalate (DnOP) and di-n-decyl phthalate (DnDP) by the slow-stirring method are reported. The water solubility was also measured for di-n-hexyl phthalate (DnHP). The log K-ow val...

Organophosphorus and Organochlorine Pesticides Bioaccumulation by Eichhornia crassipes in Irrigation Canals in an Urban Agricultural System.

PubMed

Mercado-Borrayo, B M; Cram Heydrich, Silke; Pérez, Irma Rosas; Hernández Quiroz, Manuel; De León Hill, Claudia Ponce

2015-01-01

A natural wetland in Mexico City Metropolitan Area is one of the main suppliers of crops and flowers, and in consequence its canals hold a high concentration of organochlorine (OC) and organophosphorus (OP) pesticides. There is also an extensive population of water hyacinth (Eichhornia crassipes), which is considered a plague; but literature suggests water hyacinth may be used as a phytoremediator. This study demonstrates bioaccumulation difference for the OC in vivo suggesting their bioaccumulation is ruled by their log K(ow), while all the OP showed bioaccumulation regardless of their log K(ow). The higher bioaccumulation factors (BAF) of the accumulated OC pesticides cannot be explained by their log K(ow), suggesting that the OC pesticides may also be transported passively into the plant. Translocation ratios showed that water hyacinth is an accumulating plant with phytoremediation potential for all organophosphorus pesticides studied and some organochlorine pesticides. An equation for free water surface wetlands with floating macrophytes, commonly used for the construction of water-cleaning wetlands, showed removal of the pesticides by the wetland with room for improvement with appropriate management.

Evaluating the Bioaccessibility of Flame Retardants in House Dust Using an In Vitro Tenax Bead-Assisted Sorptive Physiologically Based Method

PubMed Central

2015-01-01

Exposure to house dust is a significant source of exposure to flame retardant chemicals (FRs), particularly in the US. Given the high exposure there is a need to understand the bioaccessibility of FRs from dust. In this study, Tenax beads (TA) encapsulated within a stainless steel insert were used as an adsorption sink to estimate the dynamic absorption of a suite of FRs commonly detected in indoor dust samples (n = 17), and from a few polyurethane foam samples for comparison. Organophosphate flame retardants (OPFRs) had the highest estimated bioaccessibility (∼80%) compared to brominated compounds (e.g., PBDEs), and values generally decreased with increasing Log Kow, with <30% bioaccessibility measured for BDE209. These measurements were in very close agreement with reported PBDE bioavailability measures from an in vivo rat exposure study using indoor dust. The bioaccessibility of very hydrophobic FRs (Log Kow > 6) in foam was much less than that in house dust, and increasing bioaccessibility was observed with decreasing particle size. In addition, we examined the stability of more labile FRs containing ester groups (e.g., OPFRs and 2-ethylhexyl-tetrabromo-benzoate (EH-TBB)) in a mock-digestive fluid matrix. No significant changes in the OPFR concentrations were observed in this fluid; however, EH-TBB was found to readily hydrolyze to tetrabromobenzoic acid (TBBA) in the intestinal fluid in the presence of lipases. In conclusion, our study demonstrates that the bioaccessibility and stability of FRs following ingestion varies by chemical and sample matrix and thus should be considered in exposure assessments. PMID:25330458

Measured and Modeled Toxicokinetics in Cultured Fish Cells and Application to In Vitro - In Vivo Toxicity Extrapolation

PubMed Central

Stadnicka-Michalak, Julita; Tanneberger, Katrin; Schirmer, Kristin; Ashauer, Roman

2014-01-01

Effect concentrations in the toxicity assessment of chemicals with fish and fish cells are generally based on external exposure concentrations. External concentrations as dose metrics, may, however, hamper interpretation and extrapolation of toxicological effects because it is the internal concentration that gives rise to the biological effective dose. Thus, we need to understand the relationship between the external and internal concentrations of chemicals. The objectives of this study were to: (i) elucidate the time-course of the concentration of chemicals with a wide range of physicochemical properties in the compartments of an in vitro test system, (ii) derive a predictive model for toxicokinetics in the in vitro test system, (iii) test the hypothesis that internal effect concentrations in fish (in vivo) and fish cell lines (in vitro) correlate, and (iv) develop a quantitative in vitro to in vivo toxicity extrapolation method for fish acute toxicity. To achieve these goals, time-dependent amounts of organic chemicals were measured in medium, cells (RTgill-W1) and the plastic of exposure wells. Then, the relation between uptake, elimination rate constants, and log KOW was investigated for cells in order to develop a toxicokinetic model. This model was used to predict internal effect concentrations in cells, which were compared with internal effect concentrations in fish gills predicted by a Physiologically Based Toxicokinetic model. Our model could predict concentrations of non-volatile organic chemicals with log KOW between 0.5 and 7 in cells. The correlation of the log ratio of internal effect concentrations in fish gills and the fish gill cell line with the log KOW was significant (r>0.85, p = 0.0008, F-test). This ratio can be predicted from the log KOW of the chemical (77% of variance explained), comprising a promising model to predict lethal effects on fish based on in vitro data. PMID:24647349

A rapidly equilibrating, thin film, passive water sampler for organic contaminants; characterization and field testing.

PubMed

St George, Tiffany; Vlahos, Penny; Harner, Tom; Helm, Paul; Wilford, Bryony

2011-02-01

Improving methods for assessing the spatial and temporal resolution of organic compound concentrations in marine environments is important to the sustainable management of our coastal systems. Here we evaluate the use of ethylene vinyl acetate (EVA) as a candidate polymer for thin-film passive sampling in waters of marine environments. Log K(EVA-W) partition coefficients correlate well (r(2) = 0.87) with Log K(OW) values for selected pesticides and polychlorinated biphenyls (PCBs) where Log K(EVA-W) = 1.04 Log K(OW) + 0.22. EVA is a suitable polymer for passive sampling due to both its high affinity for organic compounds and its ease of coating at sub-micron film thicknesses on various substrates. Twelve-day field deployments were effective in detecting target compounds with good precision making EVA a potential multi-media fugacity meter. Published by Elsevier Ltd.

A comparison of octanol-water partitioning between organic chemicals and their metabolites in mammals.

PubMed

Pirovano, Alessandra; Borile, Nicolò; Jan Hendriks, A

2012-08-01

Bioaccumulation models take various elimination and uptake processes into account, estimating rates from chemical lipophilicity, expressed as the octanol-water partition ratio (K(ow)). Here, we focussed on metabolism, which transforms parent compounds into usually more polar metabolites, thus enhancing elimination. The aim of this study was to quantify the change in lipophilicity of relevant organic pollutants undergoing various biotransformation reactions in mammals. We considered oxidation reactions catalyzed by three enzyme groups: cytochrome P450 (CYP), alcohol dehydrogenase (ADH), and aldehyde dehydrogenase (ALDH). Estimated logK(ow) values of a selected dataset of parent compounds were compared with the logK(ow) of their first metabolites. The logK(ow) decreased by a factor that varies between 0 and -2, depending on the metabolic pathway. For reactions mediated by CYP, the decrease in K(ow) was one order of magnitude for hydroxylated and epoxidated compounds and two orders of magnitude for dihydroxylated and sulphoxidated xenobiotics. On the other hand, no significant change in lipophilicity was observed for compounds N-hydroxylated by CYP and for alcohols and aldehydes metabolized by ADH and ALDH. These trends could be anticipated by the calculus method of logK(ow). Yet, they were validated using experimental logK(ow) values, when available. These relationships estimate the extent to which the elimination of pollutants is increased by biotransformation. Thus, the quantification of the K(ow) reduction can be considered as a first necessary step in an alternative approach to anticipate biotransformation rates, which are hard to estimate with existing methods. Copyright © 2012 Elsevier Ltd. All rights reserved.

Assessment of rate of drug release from oil vehicle using a rotating dialysis cell.

PubMed

Larsen, D H; Fredholt, K; Larsen, C

2000-09-01

The rate constants for transfer of model compounds (naproxen and lidocaine) from oily vehicle (Viscoleo) to aqueous buffer phases were determined by use of the rotating dialysis cell. Release studies were done for the partly ionized compounds at several pH values. A correlation between the overall first-order rate constant related to attainment of equilibrium, k(obs), and the pH-dependent distribution coefficient, D, determined between oil vehicle and aqueous buffer was established according to the equation: logk(obs)=-0.71 logD-0.22 (k(obs) in h(-1)). Based on this correlation it was suggested that the rate constant of a weak electrolyte at a specified D value could be considered equal to the k(obs) value for a non-electrolyte possessing a partition coefficient, P(app), the magnitude of which was equal to D. Specific rate constants k(ow) and k(wo) were calculated from the overall rate constant and the pH-dependent distribution coefficient. The rate constant representing the transport from oily vehicle to aqueous phase, k(ow), was found to be significantly influenced by the magnitude of the partition coefficient P(app) according to: logk(ow)=-0.71 logP(app)-log(P(app)+1)-0.22 (k(ow) in h(-1)).

Physico-chemical measurements of CL-20 for environmental applications. Comparison with RDX and HMX.

PubMed

Monteil-Rivera, Fanny; Paquet, Louise; Deschamps, Stéphane; Balakrishnan, Vimal K; Beaulieu, Chantale; Hawari, Jalal

2004-01-30

CL-20 is a polycyclic energetic nitramine, which may soon replace the monocyclic nitramines RDX and HMX, because of its superior explosive performance. Therefore, to predict its environmental fate, analytical and physico-chemical data must be made available. An HPLC technique was thus developed to measure CL-20 in soil samples based on the US Environmental Protection Agency method 8330. We found that the soil water content and aging (21 days) had no effect on the recoveries (>92%) of CL-20, provided that the extracts were kept acidic (pH 3). The aqueous solubility of CL-20 was poor (3.6 mg l(-1) at 25 degrees C) and increased with temperature to reach 18.5 mg l(-1) at 60 degrees C. The octanol-water partition coefficient of CL-20 (log KOW = 1.92) was higher than that of RDX (log KOW = 0.90) and HMX (log KOW = 0.16), indicating its higher affinity to organic matter. Finally, CL-20 was found to decompose in non-acidified water upon contact with glass containers to give NO2- (2 equiv.), N2O (2 equiv.), and HCOO- (2 equiv.). The experimental findings suggest that CL-20 should be less persistent in the environment than RDX and HMX.

Uptake of pesticides from water by curly waterweed Lagarosiphon major and lesser duckweed Lemna minor.

PubMed

de Carvalho, Renato F; Bromilow, Richard H; Greenwood, Richard

2007-08-01

The uptake of pesticides from water by two aquatic plants, the submersed Lagarosiphon major (Ridley) Moss and the floating duckweed Lemna minor L., was measured over periods of up to 72 h. Twelve non-ionised pesticides and analogues, chosen to span a wide range of physicochemical properties, and one analogue (3,5-D) of the phenoxyacetic acid herbicide 2,4-D were studied. Concentrations of the parent compound were determined in the plants following extraction and separation by chromatography. Quantification was by liquid scintillation counting for the (14)C-labelled compounds and by high-performance liquid chromatography for the four non-radiolabelled commercial pesticides. Uptake for all compound and plant combinations had reached equilibrium by 24 h. Accumulation of compound in the plant could be described well for most non-ionised compounds by equilibration into the aqueous phase in the plant cells together with partitioning onto the plant solids, this latter process becoming dominant in Lagarosiphon for compounds with log K(ow) > 1 and in Lemna for compounds with log K(ow) > 1.8. Lipophilic compounds with log K(ow) > 4 were concentrated more than 100-fold on a fresh-weight basis. However, the uptake of isoproturon and chlorotoluron was up to threefold less than expected from their K(ow) values, and their behaviour was better explained using solvation descriptors. Uptake of the acid 3,5-D was dependent on solution pH, this compound being strongly taken up at lower pH by the process of ion trapping, as previously observed in barley roots. Aquatic vegetation can thus rapidly accumulate pesticides, and could be an important sink especially for lipophilic pesticides reaching well-vegetated waters. Copyright (c) 2007 Society of Chemical Industry

The search for reliable aqueous solubility (Sw) and octanol-water partition coefficient (Kow) data for hydrophobic organic compounds; DDT and DDE as a case study

USGS Publications Warehouse

Pontolillo, James; Eganhouse, R.P.

2001-01-01

The accurate determination of an organic contaminant?s physico-chemical properties is essential for predicting its environmental impact and fate. Approximately 700 publications (1944?2001) were reviewed and all known aqueous solubilities (Sw) and octanol-water partition coefficients (Kow) for the organochlorine pesticide, DDT, and its persistent metabolite, DDE were compiled and examined. Two problems are evident with the available database: 1) egregious errors in reporting data and references, and 2) poor data quality and/or inadequate documentation of procedures. The published literature (particularly the collative literature such as compilation articles and handbooks) is characterized by a preponderance of unnecessary data duplication. Numerous data and citation errors are also present in the literature. The percentage of original Sw and Kow data in compilations has decreased with time, and in the most recent publications (1994?97) it composes only 6?26 percent of the reported data. The variability of original DDT/DDE Sw and Kow data spans 2?4 orders of magnitude, and there is little indication that the uncertainty in these properties has declined over the last 5 decades. A criteria-based evaluation of DDT/DDE Sw and Kow data sources shows that 95?100 percent of the database literature is of poor or unevaluatable quality. The accuracy and reliability of the vast majority of the data are unknown due to inadequate documentation of the methods of determination used by the authors. [For example, estimates of precision have been reported for only 20 percent of experimental Sw data and 10 percent of experimental Kow data.] Computational methods for estimating these parameters have been increasingly substituted for direct or indirect experimental determination despite the fact that the data used for model development and validation may be of unknown reliability. Because of the prevalence of errors, the lack of methodological documentation, and unsatisfactory data quality, the reliability of the DDT/ DDE Sw and Kow database is questionable. The nature and extent of the errors documented in this study are probably indicative of a more general problem in the literature of hydrophobic organic compounds. Under these circumstances, estimation of critical environmental parameters on the basis of Sw and Kow (for example, bioconcentration factors, equilibrium partition coefficients) is inadvisable because it will likely lead to incorrect environmental risk assessments. The current state of the database indicates that much greater efforts are needed to: 1) halt the proliferation of erroneous data and references, 2) initiate a coordinated program to develop improved methods of property determination, 3) establish and maintain consistent reporting requirements for physico-chemical property data, and 4) create a mechanism for archiving reliable data for widespread use in the scientific/regulatory community.

Uptake of PAHs into polyoxymethylene and application to oil-soot (lampblack)-impacted soil samples.

PubMed

Hong, Lei; Luthy, Richard G

2008-05-01

Polyoxymethylene (POM) is a polymeric material used increasingly in passive sampling of hydrophobic organic contaminants such as PAHs and PCBs in soils and sediments. In this study, we examined the sorption behavior of 12 PAH compounds to POM and observed linear isotherms spanning two orders of magnitude of aqueous concentrations. Uptake kinetic studies performed in batch systems for up to 54 d with two different volume ratios of POM-to-aqueous phase were evaluated with coupled diffusion and mass transfer models to simulate the movement of PAHs during the uptake process and to assess the physicochemical properties and experimental conditions that control uptake rates. Diffusion coefficients of PAHs in POM were estimated to be well correlated with diffusants' molecular weights as D(POM) proportional, variant(MW)(-3), descending from 2.3 x 10(-10) cm(2) s(-1) for naphthalene to 7.0 x 10(-11) cm(2) s(-1) for pyrene. The uptake rates for PAHs with log K(ow)<5.8 were controlled by the POM phase and the hydrophobicity of PAH compounds. For more hydrophobic PAH compounds, the aqueous boundary layer played an increasingly important role in determining the overall mass transfer rate. The POM partitioning technique was demonstrated to agree well with two other procedures for measuring PAH soil-water distribution coefficients in oil-soot (lampblack) containing soil samples.

n-Alcohol/Water Partition Coefficients for Decachlorobiphenyl (PCB 209)

EPA Science Inventory

Measurements of n-octanol/water partition coefficients (Kow) for highly hydrophobic chemicals are extremely difficult and are rarely made, in part due to the large volumes of water typically needed to quantify these compounds in the aqueous phase. An extrapolation approach using ...

Solvent-assisted stir bar sorptive extraction by using swollen polydimethylsiloxane for enhanced recovery of polar solutes in aqueous samples: Application to aroma compounds in beer and pesticides in wine.

PubMed

Ochiai, Nobuo; Sasamoto, Kikuo; David, Frank; Sandra, Pat

2016-07-15

A novel solvent-assisted stir bar sorptive extraction (SA-SBSE) technique was developed for enhanced recovery of polar solutes in aqueous samples. A conventional PDMS stir bar was swollen in several solvents with log Kow ranging from 1.0 to 3.5 while stirring for 30min prior to extraction. After extraction, thermal desorption - gas chromatography - (tandem) mass spectrometry (TD-GC-(MS/)MS) or liquid desorption - large volume injection (LD-LVI)-GC-MS were performed. An initial study involved investigation of potential solvents for SA-SBSE by weighing of the residual solvent in the swollen PDMS stir bar before and after extraction. Compared to conventional SBSE, SA-SBSE using diethyl ether, methyl isobutyl ketone, dichloromethane, diisopropyl ether and toluene provided higher recoveries from water samples for test solutes with log Kow<2.5. For SA-SBSE using dichloromethane, recoveries were improved by factors of 1.4-4.1, while maintaining or even improving the recoveries for test solutes with log Kow>2.5. The performance of the SA-SBSE method using dichloromethane, diisopropyl ether, and cyclohexane is illustrated with analyses of aroma compounds in beer and of pesticides in wine. Copyright © 2016 The Authors. Published by Elsevier B.V. All rights reserved.

40 CFR Appendix B to Part 132 - Great Lakes Water Quality Initiative

Code of Federal Regulations, 2011 CFR

2011-07-01

... WATER QUALITY GUIDANCE FOR THE GREAT LAKES SYSTEM Pt. 132, App. B Appendix B to Part 132—Great Lakes Water Quality Initiative Methodology for Deriving Bioaccumulation Factors Great Lakes States and Tribes... system. For log KOW, the log of the octanol-water partition coefficient is a base 10 logarithm. Uptake...

40 CFR Appendix B to Part 132 - Great Lakes Water Quality Initiative

Code of Federal Regulations, 2010 CFR

2010-07-01

... WATER QUALITY GUIDANCE FOR THE GREAT LAKES SYSTEM Pt. 132, App. B Appendix B to Part 132—Great Lakes Water Quality Initiative Methodology for Deriving Bioaccumulation Factors Great Lakes States and Tribes... system. For log KOW, the log of the octanol-water partition coefficient is a base 10 logarithm. Uptake...

Trophic magnification of organic chemicals: A global synthesis

USGS Publications Warehouse

Walters, David; Jardine, T.D.; Cade, Brian S.; Kidd, K.A.; Muir, D.C.G.; Leipzig-Scott, Peter C.

2016-01-01

Production of organic chemicals (OCs) is increasing exponentially, and some OCs biomagnify through food webs to potentially toxic levels. Biomagnification under field conditions is best described by trophic magnification factors (TMFs; per trophic level change in log-concentration of a chemical) which have been measured for more than two decades. Syntheses of TMF behavior relative to chemical traits and ecosystem properties are lacking. We analyzed >1500 TMFs to identify OCs predisposed to biomagnify and to assess ecosystem vulnerability. The highest TMFs were for OCs that are slowly metabolized by animals (metabolic rate kM < 0.01 day–1) and are moderately hydrophobic (log KOW 6–8). TMFs were more variable in marine than freshwaters, unrelated to latitude, and highest in food webs containing endotherms. We modeled the probability that any OC would biomagnify as a combined function of KOW and kM. Probability is greatest (∼100%) for slowly metabolized compounds, regardless of KOW, and lowest for chemicals with rapid transformation rates (kM > 0.2 day–1). This probabilistic model provides a new global tool for screening existing and new OCs for their biomagnification potential.

Uptake and Translocation of Lesser-Chlorinated Polychlorinated Biphenyls (PCBs) in Whole Hybrid Poplar Plants after Hydroponic Exposure

PubMed Central

Liu, Jiyan; Schnoor, Jerald L.

2009-01-01

Mono-, di-, tri-, and tetra-chlorinated polychlorinated biphenyls (PCBs) are congeners with greater volatility which remain in air, soils and sediments requiring treatment. In this study, the fate of these PCBs was investigated within whole poplar plants (Populus deltoides x nigra, DN34) with application for a treatment system such as a confined disposal facility for dredged material. Whole hybrid poplars were exposed hydroponically to a mixture of five congeners, common in the environment, having one to four chlorine atoms per molecule. Results indicated that PCB 3, 15, 28, 52, and 77 were initially sorbed to the root systems. The Root Concentration Factor (RCF) of PCBs during the exposure was calculated and correlated with Kow. PCB congeners were taken up by the roots of hybrid poplar, and the translocation of PCBs to stems was inversely related to congener hydrophobicity (Log Kow). PCB 3 and 15 were translocated to the upper stem at small but significant rates. PCB 28 was translocated to the wood of the main stem but no farther; translocation from the roots was not detected for PCB 52 and 77. The distribution of PCBs within poplars was determined, and mass balances were completed to within 15% for each chemical except for PCB 3, the most volatile congener. This is the first report on the transport of PCBs through whole plants designed for use in treatment at disposal facilities. PMID:18793792

Evaluation of alternative approaches for measuring n-octanol/water partition coefficients for methodologically challenging chemicals (MCCs)

EPA Science Inventory

Measurements of n-octanol/water partition coefficients (KOW) for highly hydrophobic chemicals, i.e., greater than 108, are extremely difficult and are rarely made, in part because the vanishingly small concentrations in the water phase require extraordinary analytical sensitivity...

Quantitative relationship between the octanol/water partition coefficient and the diffusion limitation of the exchange between adipose and blood

PubMed Central

2010-01-01

Background The goal of physiologically based pharmacokinetics (PBPK) is to predict drug kinetics from an understanding of the organ/blood exchange. The standard approach is to assume that the organ is "flow limited" which means that the venous blood leaving the organ equilibrates with the well-stirred tissue compartment. Although this assumption is valid for most solutes, it has been shown to be incorrect for several very highly fat soluble compounds which appear to be "diffusion limited". This paper describes the physical basis of this adipose diffusion limitation and its quantitative dependence on the blood/water (Kbld-wat) and octanol/water (Kow) partition coefficient. Methods Experimental measurements of the time dependent rat blood and adipose concentration following either intravenous or oral input were used to estimate the "apparent" adipose perfusion rate (FA) assuming that the tissue is flow limited. It is shown that the ratio of FA to the anatomic perfusion rate (F) provides a measure of the diffusion limitation. A quantitative relationship between this diffusion limitation and Kbld-wat and Kow is derived. This analysis was applied to previously published data, including the Oberg et. al. measurements of the rat plasma and adipose tissue concentration following an oral dose of a mixture of 13 different polychlorinated biphenyls. Results Solutes become diffusion limited at values of log Kow greater than about 5.6, with the adipose-blood exchange rate reduced by a factor of about 30 for a solute with a log Kow of 7.36. Quantitatively, a plot of FA/F versus Kow is well described assuming an adipose permeability-surface area product (PS) of 750/min. This PS corresponds to a 0.14 micron aqueous layer separating the well-stirred blood from the adipose lipid. This is approximately equal to the thickness of the rat adipose capillary endothelium. Conclusions These results can be used to quantitate the adipose-blood diffusion limitation as a function of Kow. This is especially important for the highly fat soluble persistent organic chemicals (e.g. polychlorinated biphenyls, dioxins) whose pharmacokinetics are primarily determined by the adipose-blood exchange kinetics. PMID:20055995

Quantitative relationship between the octanol/water partition coefficient and the diffusion limitation of the exchange between adipose and blood.

PubMed

Levitt, David G

2010-01-07

The goal of physiologically based pharmacokinetics (PBPK) is to predict drug kinetics from an understanding of the organ/blood exchange. The standard approach is to assume that the organ is "flow limited" which means that the venous blood leaving the organ equilibrates with the well-stirred tissue compartment. Although this assumption is valid for most solutes, it has been shown to be incorrect for several very highly fat soluble compounds which appear to be "diffusion limited". This paper describes the physical basis of this adipose diffusion limitation and its quantitative dependence on the blood/water (Kbld-wat) and octanol/water (Kow) partition coefficient. Experimental measurements of the time dependent rat blood and adipose concentration following either intravenous or oral input were used to estimate the "apparent" adipose perfusion rate (FA) assuming that the tissue is flow limited. It is shown that the ratio of FA to the anatomic perfusion rate (F) provides a measure of the diffusion limitation. A quantitative relationship between this diffusion limitation and Kbld-wat and Kow is derived. This analysis was applied to previously published data, including the Oberg et. al. measurements of the rat plasma and adipose tissue concentration following an oral dose of a mixture of 13 different polychlorinated biphenyls. Solutes become diffusion limited at values of log Kow greater than about 5.6, with the adipose-blood exchange rate reduced by a factor of about 30 for a solute with a log Kow of 7.36. Quantitatively, a plot of FA/F versus Kow is well described assuming an adipose permeability-surface area product (PS) of 750/min. This PS corresponds to a 0.14 micron aqueous layer separating the well-stirred blood from the adipose lipid. This is approximately equal to the thickness of the rat adipose capillary endothelium. These results can be used to quantitate the adipose-blood diffusion limitation as a function of Kow. This is especially important for the highly fat soluble persistent organic chemicals (e.g. polychlorinated biphenyls, dioxins) whose pharmacokinetics are primarily determined by the adipose-blood exchange kinetics.

Adsorption characteristics of selected pharmaceuticals and an endocrine disrupting compound-Naproxen, carbamazepine and nonylphenol-on activated carbon.

PubMed

Yu, Zirui; Peldszus, Sigrid; Huck, Peter M

2008-06-01

The adsorption of two representative pharmaceutically active compounds (PhACs) (naproxen and carbamazepine) and one endocrine disrupting compound (nonylphenol) were evaluated on two types of activated carbon. When determining their isotherms at environmentally relevant concentration levels, it was found that at this low concentration range (10-800 ng/L), removals of the target compounds were contrary to expectations based on their hydrophobicity. Nonylphenol (log K(ow) 5.8) was most poorly adsorbed, whereas carbamazepine (log K(ow) 2.45) was most adsorbable. Nonylphenol Freundlich isotherms at this very low concentration range had a much higher 1/n compared to isotherms at much higher concentrations. This indicates that extrapolation from an isotherm obtained at a high concentration range to predict the adsorption of nonylphenol at a concentration well below the range of the original isotherm, leads to a substantial overestimation of its removals. Comparison of isotherms for the target compounds to those for other conventional micropollutants suggested that naproxen and carbamazepine could be effectively removed by applying the same dosage utilized to remove odorous compounds (geosmin and MIB) at very low concentrations. The impact of competitive adsorption by background natural organic matter (NOM) on the adsorption of the target compounds was quantified by using the ideal adsorbed solution theory (IAST) in combination with the equivalent background compound (EBC) approach. The fulfilment of the requirements for applying the simplified IAST-EBC model, which leads to the conclusion that the percentage removal of the target compounds at a given carbon dosage is independent of the initial contaminant concentration, was confirmed for the situation examined in the paper. On this basis it is suggested that the estimated minimum carbon usage rates (CURs) to achieve 90% removal of these emerging contaminants would be valid at concentrations of less than 500 ng/L in natural water.

Contribution of the Hair Follicular Pathway to Total Skin Permeation of Topically Applied and Exposed Chemicals

PubMed Central

Mohd, Fadli; Todo, Hiroaki; Yoshimoto, Masato; Yusuf, Eddy; Sugibayashi, Kenji

2016-01-01

Generally, the blood and skin concentration profiles and steady-state skin concentration of topically applied or exposed chemicals can be calculated from the in vitro skin permeation profile. However, these calculation methods are particularly applicable to chemicals for which the main pathway is via the stratum corneum. If the contribution of hair follicles to the total skin permeation of chemicals can be obtained in detail, their blood and skin concentrations can be more precisely predicted. In the present study, the contribution of the hair follicle pathway to the skin permeation of topically applied or exposed chemicals was calculated from the difference between their permeability coefficients through skin with and without hair follicle plugging, using an in vitro skin permeation experiment. The obtained results reveal that the contribution of the hair follicle pathway can be predicted by using the chemicals’ lipophilicity. For hydrophilic chemicals (logarithm of n-octanol/water partition coefficient (log Ko/w) < 0), a greater reduction of permeation due to hair follicle plugging was observed than for lipophilic chemicals (log Ko/w ≥ 0). In addition, the ratio of this reduction was decreased with an increase in log Ko/w. This consideration of the hair follicle pathway would be helpful to investigate the efficacy and safety of chemicals after topical application or exposure to them because skin permeation and disposition should vary among skins in different body sites due to differences in the density of hair follicles. PMID:27854289

Partitioning of fluorotelomer alcohols to octanol and different sources of dissolved organic carbon.

PubMed

Carmosini, Nadia; Lee, Linda S

2008-09-01

Interest in the environmental fate of fluorotelomer alcohols (FTOHs) has spurred efforts to understand their equilibrium partitioning behavior. Experimentally determined partition coefficients for FTOHs between soil/water and air/water have been reported, but direct measurements of partition coefficients for dissolved organic carbon (DOC)/water (K(doc)) and octanol/ water(K(ow)) have been lacking. Here we measured the partitioning of 8:2 and 6:2 FTOH between one or more types of DOC and water using enhanced solubility or dialysis bag techniques, and also quantified K(ow) values for 4:2 to 8:2 FTOH using a batch equilibration method. The range in measured log K(doc) values for 8:2 FTOH using the enhanced solubility technique with DOC derived from two soils, two biosolids, and three reference humic acids is 2.00-3.97 with the lowest values obtained for the biosolids and an average across all other DOC sources (biosolid DOC excluded) of 3.54 +/- 0.29. For 6:2 FTOH and Aldrich humic acid, a log K(doc) value of 1.96 +/- 0.45 was measured using the dialysis technique. These average values are approximately 1 to 2 log units lower than previously indirectly estimated K(doc) values. Overall, the affinity for DOC tends to be slightly lower than that for particulate soil organic carbon. Measured log K(ow) values for 4:2 (3.30 +/- 0.04), 6:2 (4.54 +/- 0.01), and 8:2 FTOH (5.58 +/- 0.06) were in good agreement with previously reported estimates. Using relationships between experimentally measured partition coefficients and C-atom chain length, we estimated K(doc) and K(ow) values for shorter and longer chain FTOHs, respectively, that we were unable to measure experimentally.

Substitution of carcinogenic solvent dichloromethane for the extraction of volatile compounds in a fat-free model food system.

PubMed

Cayot, Nathalie; Lafarge, Céline; Bou-Maroun, Elias; Cayot, Philippe

2016-07-22

Dichloromethane is known as a very efficient solvent, but, as other halogenated solvents, is recognized as a hazardous product (CMR substance). The objective of the present work is to propose substitution solvent for the extraction of volatile compounds. The most important physico-chemical parameters in the choice of an appropriate extraction solvent of volatile compounds are reviewed. Various solvents are selected on this basis and on their hazard characteristics. The selected solvents, safer than dichloromethane, are compared using the extraction efficiency of volatile compounds from a model food product able to interact with volatile compounds. Volatile compounds with different hydrophobicity are used. High extraction yields were positively correlated with high boiling points and high Log Kow values of volatile compounds. Mixtures of solvents such as azeotrope propan-2-one/cyclopentane, azeotrope ethyl acetate/ethanol, and mixture ethyl acetate/ethanol (3:1, v/v) gave higher extraction yields than those obtained with dichloromethane. Copyright © 2016 Elsevier B.V. All rights reserved.

A combined QSAR and partial order ranking approach to risk assessment.

PubMed

Carlsen, L

2006-04-01

QSAR generated data appear as an attractive alternative to experimental data as foreseen in the proposed new chemicals legislation REACH. A preliminary risk assessment for the aquatic environment can be based on few factors, i.e. the octanol-water partition coefficient (Kow), the vapour pressure (VP) and the potential biodegradability of the compound in combination with the predicted no-effect concentration (PNEC) and the actual tonnage in which the substance is produced. Application of partial order ranking, allowing simultaneous inclusion of several parameters leads to a mutual prioritisation of the investigated substances, the prioritisation possibly being further analysed through the concept of linear extensions and average ranks. The ranking uses endpoint values (log Kow and log VP) derived from strictly linear 'noise-deficient' QSAR models as input parameters. Biodegradation estimates were adopted from the BioWin module of the EPI Suite. The population growth impairment of Tetrahymena pyriformis was used as a surrogate for fish lethality.

Transplacental transfer of polychlorinated biphenyls and polybrominated diphenyl ethers in arctic beluga whales (Delphinapterus leucas).

PubMed

Desforges, Jean-Pierre W; Ross, Peter S; Loseto, Lisa L

2012-02-01

This study found that arctic beluga whales (Delphinapterus leucas) transferred, on average, 11.4% (7.5 mg) and 11.1% (0.1 mg) of their polychlorinated biphenyl (PCB) and polybrominated diphenyl ether (PBDE) blubber burden to their near-term fetuses. A single physicochemical parameter, log K(OW), largely explained this transplacental transfer for PCBs (r(2) =0.79, p < 0.00001) and PBDEs (r(2) = 0.37, p = 0.007), with congeners having a log K(OW) < 6.5 preferentially transferred to the fetus. Blubber concentrations of 257 ng/g lipid weight (lw) PCBs and 3.8 ng/g (lw) PBDEs in beluga fetuses highlights the exposure to endocrine-disrupting compounds during a critical developmental stage. The implications of detecting these levels of legacy PCBs and the flame retardant PBDEs in unborn arctic beluga are unclear. Copyright © 2011 SETAC.

Multi-stir bar sorptive extraction for analysis of odor compounds in aqueous samples.

PubMed

Ochiai, Nobuo; Sasamoto, Kikuo; Ieda, Teruyo; David, Frank; Sandra, Pat

2013-11-08

As reproducible coating of stir bars with more polar phases was found to be very difficult, a supporting grid was used in the development of an ethyleneglycol-modified Silicone (EG Silicone) coated stir bar. This new polar coating showed good performance for the extraction of polar solutes, but long term use also showed degradation of the coating due to friction while stirring. In order to address the lower robustness of the EG Silicone stir bar which has a much softer coating compared to a conventional polydimethylsiloxane (PDMS) stir bar, a novel SBSE procedure termed multi-SBSE ((m)SBSE) was developed. (m)SBSE consists of the robust PDMS stir bar stirring at the bottom of the vial and the EG Silicone stir bar attached on the inner side wall of the vial (a magnetic clip is used for the set-up). After extraction, the two stir bars are placed in a single glass desorption liner and are simultaneously thermally desorbed. The desorbed compounds were analyzed by thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS). Compared to conventional SBSE, (m)SBSE provides more uniform enrichment of a wide range of odor compounds in aqueous sample since both stir bars can complement each other, while eliminating the damage of the EG Silicone phase during the extraction. The robustness of the EG Silicone stir bar was dramatically increased and more than 30 extraction and desorption cycles were possible without loss in performance. The recoveries for polar solutes such as 2-acetyl pyrrole (logKow: 0.55), benzyl alcohol (logKow: 1.08), guaiacol (logKow: 1.34), and indole (logKow: 2.05) were increased by a factor of about 2-7. The (m)SBSE-TD-GC-MS method showed good linearity (r(2)>0.9913) and high sensitivity (limit of detection: 0.011-0.071 ng mL(-1)) for the test compounds spiked in water. The feasibility and benefit of the method was demonstrated with analysis of odor compounds in roasted green tea. The normalized areas obtained from (m)SBSE showed the best enrichment for most of the selected compounds compared to conventional SBSE using the PDMS stir bar or the EG Silicone stir bar. Fifteen compounds were determined in the range of 0.15-210 ng mL(-1) (RSD<14%, n=6). Copyright © 2013 Elsevier B.V. All rights reserved.

Controlled field evaluation of water flow rate effects on sampling polar organic compounds using polar organic chemical integrative samplers.

PubMed

Li, Hongxia; Vermeirssen, Etiënne L M; Helm, Paul A; Metcalfe, Chris D

2010-11-01

The uptake of polar organic contaminants into polar organic chemical integrative samplers (POCIS) varies with environmental factors, such as water flow rate. To evaluate the influence of water flow rate on the uptake of contaminants into POCIS, flow-controlled field experiments were conducted with POCIS deployed in channel systems through which treated sewage effluent flowed at rates between 2.6 and 37 cm/s. Both pharmaceutical POCIS and pesticide POCIS were exposed to effluent for 21 d and evaluated for uptake of pharmaceuticals and personal care products (PPCPs) and endocrine disrupting substances (EDS). The pesticide POCIS had higher uptake rates for PPCPs and EDS than the pharmaceutical POCIS, but there are some practical advantages to using pharmaceutical POCIS. The uptake of contaminants into POCIS increased with flow rate, but these effects were relatively small (i.e., less than twofold) for most of the test compounds. There was no relationship observed between the hydrophobicity (log octanol/water partition coefficient, log K(OW)) of model compounds and the effects of flow rate on the uptake kinetics by POCIS. These data indicate that water flow rate has a relatively minor influence on the accumulation of PPCPs and EDS into POCIS. © 2010 SETAC.

Critical evaluation of a simple retention time predictor based on LogKow as a complementary tool in the identification of emerging contaminants in water.

PubMed

Bade, Richard; Bijlsma, Lubertus; Sancho, Juan V; Hernández, Felix

2015-07-01

There has been great interest in environmental analytical chemistry in developing screening methods based on liquid chromatography-high resolution mass spectrometry (LC-HRMS) for emerging contaminants. Using HRMS, compound identification relies on the high mass resolving power and mass accuracy attainable by these analyzers. When dealing with wide-scope screening, retention time prediction can be a complementary tool for the identification of compounds, and can also reduce tedious data processing when several peaks appear in the extracted ion chromatograms. There are many in silico, Quantitative Structure-Retention Relationship methods available for the prediction of retention time for LC. However, most of these methods use commercial software to predict retention time based on various molecular descriptors. This paper explores the applicability and makes a critical discussion on a far simpler and cheaper approach to predict retention times by using LogKow. The predictor was based on a database of 595 compounds, their respective LogKow values and a chromatographic run time of 18min. Approximately 95% of the compounds were found within 4.0min of their actual retention times, and 70% within 2.0min. A predictor based purely on pesticides was also made, enabling 80% of these compounds to be found within 2.0min of their actual retention times. To demonstrate the utility of the predictors, they were successfully used as an additional tool in the identification of 30 commonly found emerging contaminants in water. Furthermore, a comparison was made by using different mass extraction windows to minimize the number of false positives obtained. Copyright © 2015 Elsevier B.V. All rights reserved.

Test battery with the human cell line activation test, direct peptide reactivity assay and DEREK based on a 139 chemical data set for predicting skin sensitizing potential and potency of chemicals.

PubMed

Takenouchi, Osamu; Fukui, Shiho; Okamoto, Kenji; Kurotani, Satoru; Imai, Noriyasu; Fujishiro, Miyuki; Kyotani, Daiki; Kato, Yoshinao; Kasahara, Toshihiko; Fujita, Masaharu; Toyoda, Akemi; Sekiya, Daisuke; Watanabe, Shinichi; Seto, Hirokazu; Hirota, Morihiko; Ashikaga, Takao; Miyazawa, Masaaki

2015-11-01

To develop a testing strategy incorporating the human cell line activation test (h-CLAT), direct peptide reactivity assay (DPRA) and DEREK, we created an expanded data set of 139 chemicals (102 sensitizers and 37 non-sensitizers) by combining the existing data set of 101 chemicals through the collaborative projects of Japan Cosmetic Industry Association. Of the additional 38 chemicals, 15 chemicals with relatively low water solubility (log Kow > 3.5) were selected to clarify the limitation of testing strategies regarding the lipophilic chemicals. Predictivities of the h-CLAT, DPRA and DEREK, and the combinations thereof were evaluated by comparison to results of the local lymph node assay. When evaluating 139 chemicals using combinations of three methods based on integrated testing strategy (ITS) concept (ITS-based test battery) and a sequential testing strategy (STS) weighing the predictive performance of the h-CLAT and DPRA, overall similar predictivities were found as before on the 101 chemical data set. An analysis of false negative chemicals suggested a major limitation of our strategies was the testing of low water-soluble chemicals. When excluded the negative results for chemicals with log Kow > 3.5, the sensitivity and accuracy of ITS improved to 97% (91 of 94 chemicals) and 89% (114 of 128). Likewise, the sensitivity and accuracy of STS to 98% (92 of 94) and 85% (111 of 129). Moreover, the ITS and STS also showed good correlation with local lymph node assay on three potency classifications, yielding accuracies of 74% (ITS) and 73% (STS). Thus, the inclusion of log Kow in analysis could give both strategies a higher predictive performance. Copyright © 2015 John Wiley & Sons, Ltd.

Partition characteristics of polycyclic aromatic hydrocarbons on soils and sediments

USGS Publications Warehouse

Chiou, C.T.; Mcgroddy, S.E.; Kile, D.E.

1998-01-01

The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., K(oc) values) are relatively invariant either for the 'clean' (uncontaminated) soils or for the clean sediments; however, the mean K(oc) values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in K(oc) are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher K(oc) values. At given K(ow) values (octanol-water), the PAHs exhibit much higher K(oc) values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower K(ow) values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log K(oc) and log K(ow) for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.The partition behavior was determined for three polycyclic aromatic hydrocarbons (PAHs), i.e., naphthalene, phenanthrene, and pyrene, from water to a range of soil and sediment samples. The measured partition coefficients of the individual PAHs between soil/sediment organic matter (SOM) and water (i.e., Koc values) are relatively invariant either for the `clean' (uncontaminated) soils or for the clean sediments; however, the mean Koc values on the sediments are about twice the values on the soils. This disparity is similar to the earlier observation for other nonpolar solutes and reflects the compositional differences between soil and sediment organic matters. No significant differences in Koc are observed between a clean coastal marine sediment and freshwater sediments. The coastal sediments that are significantly impacted by organic contaminants exhibit higher Koc values. At given Kow values (octanol-water), the PAHs exhibit much higher Koc values than other relatively nonpolar solutes (e.g., chlorinated hydrocarbons). This effect is shown to result from the enhanced partition of PAHs to SOM rather than from lower Kow values of PAHs at given supercooled liquid solute solubilities in water. The enhanced partition of PAHs over other nonpolar solutes in SOM provides an account of the markedly different correlations between log Koc and log Kow for PAHs and for other nonpolar solutes. The improved partition of PAHs in SOM stems apparently from the enhanced compatibility of their cohesive energy densities with those of the aromatic components in SOM. The approximate aromatic fraction in soil/sediment organic matter has been assessed by solid-state 13C-NMR spectroscopy.

Direct calculation of 1-octanol-water partition coefficients from adaptive biasing force molecular dynamics simulations.

PubMed

Bhatnagar, Navendu; Kamath, Ganesh; Chelst, Issac; Potoff, Jeffrey J

2012-07-07

The 1-octanol-water partition coefficient log K(ow) of a solute is a key parameter used in the prediction of a wide variety of complex phenomena such as drug availability and bioaccumulation potential of trace contaminants. In this work, adaptive biasing force molecular dynamics simulations are used to determine absolute free energies of hydration, solvation, and 1-octanol-water partition coefficients for n-alkanes from methane to octane. Two approaches are evaluated; the direct transfer of the solute from 1-octanol to water phase, and separate transfers of the solute from the water or 1-octanol phase to vacuum, with both methods yielding statistically indistinguishable results. Calculations performed with the TIP4P and SPC∕E water models and the TraPPE united-atom force field for n-alkanes show that the choice of water model has a negligible effect on predicted free energies of transfer and partition coefficients for n-alkanes. A comparison of calculations using wet and dry octanol phases shows that the predictions for log K(ow) using wet octanol are 0.2-0.4 log units lower than for dry octanol, although this is within the statistical uncertainty of the calculation.

The Installation Restoration Program Toxicology Guide. Volume 3

DTIC Science & Technology

1987-06-01

organ because of injury or disease. log Kow Log of the octanol-water partition coefficient. Lower The lowest concentration of the material in air which...involved in clotting. SGOT Serum glutamic oxalacetic transaminase, an enzyme released into the serum as the result of tissue injury , especially injury ...to the heart and/or liver. SGPT Serum glutamic pyruvic transaminase, an enzyme % released into the serum as a result of tissue injury , 1: especially

ENANTIOSELECTIVE ELIMINATION OF FIPRONIL AND SELECTED ORGANOCHLORINES BY RAINBOW TROUT (ONCORHYNCHUS MYKISS)

EPA Science Inventory

Fipronil is a phenylpyrazole pesticide widely used in applications such as rice culture, turf grass management, and residential pest control with a high probability to contaminate aquatic environments. Fipronil has moderate partitioning (log Kow = 4.01) for accumulation in biota...

Aquatic toxicity of acrylates and methacrylates: quantitative structure-activity relationships based on Kow and LC50

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

Reinert, K.H.

1987-12-01

Recent EPA scrutiny of acrylate and methacrylate monomers has resulted in restrictive consent orders and Significant New Use Rules under the Toxic Substances Control Act, based on structure-activity relationships using mouse skin painting studies. The concern is centered on human health issues regarding worker and consumer exposure. Environmental issues, such as aquatic toxicity, are still of concern. Understanding the relationships and environmental risks to aquatic organisms may improve the understanding of the potential risks to human health. This study evaluates the quantitative structure-activity relationships from measured log Kow's and log LC50's for Pimephales promelas (fathead minnow) and Carassius auratus (goldfish).more » Scientific support of the current regulations is also addressed. Two monomer classes were designated: acrylates and methacrylates. Spearman rank correlation and linear regression were run. Based on this study, an ecotoxicological difference exists between acrylates and methacrylates. Regulatory activities and scientific study should reflect this difference.« less

In vitro biotransformation rates in fish liver S9: effect of dosing techniques.

PubMed

Lee, Yung-Shan; Lee, Danny H Y; Delafoulhouze, Maximilien; Otton, S Victoria; Moore, Margo M; Kennedy, Chris J; Gobas, Frank A P C

2014-08-01

In vitro biotransformation assays are currently being explored to improve estimates of bioconcentration factors of potentially bioaccumulative organic chemicals in fish. The present study compares thin-film and solvent-delivery dosing techniques as well as single versus multiple chemical dosing for measuring biotransformation rates of selected polycyclic aromatic hydrocarbons in rainbow trout (Oncorhynchus mykiss) liver S9. The findings show that biotransformation rates of very hydrophobic substances can be accurately measured in thin-film sorbent-dosing assays from concentration-time profiles in the incubation medium but not from those in the sorbent phase because of low chemical film-to-incubation-medium mass-transfer rates at the incubation temperature of 13.5 °C required for trout liver assays. Biotransformation rates determined by thin-film dosing were greater than those determined by solvent-delivery dosing for chrysene (octanol-water partition coefficient [KOW ] =10(5.60) ) and benzo[a]pyrene (KOW  =10(6.04) ), whereas there were no statistical differences in pyrene (KOW  =10(5.18) ) biotransformation rates between the 2 methods. In sorbent delivery-based assays, simultaneous multiple-chemical dosing produced biotransformation rates that were not statistically different from those measured in single-chemical dosing experiments for pyrene and benzo[a]pyrene but not for chrysene. In solvent-delivery experiments, multiple-chemical dosing produced biotransformation rates that were much smaller than those in single-chemical dosing experiments for all test chemicals. While thin-film sorbent-phase and solvent delivery-based dosing methods are both suitable methods for measuring biotransformation rates of substances of intermediate hydrophobicity, thin-film sorbent-phase dosing may be more suitable for superhydrophobic chemicals. © 2014 SETAC.

Reduction of chlortetracycline residues in manure from therapeutically-treated beef calves

USDA-ARS?s Scientific Manuscript database

The heavily-used antibacterials, triclosan (TCS) and triclocarban (TCC) are common contaminants of biosolids that are accumulated and adsorbed into waste-water treatment plants. These compounds are highly persistent because they present high octanol-water partitioning coefficients (log10 Kow of 4.9...

Rejection of organic micro-pollutants from water by a tubular, hydrophilic pervaporative membrane designed for irrigation applications.

PubMed

Sule, May N; Templeton, Michael R; Bond, Tom

2016-01-01

The links between chemical properties, including those relating to molecular size, solubility, hydrophobicity and vapour pressure, and rejection of model aromatic micro-pollutants by a tubular, hydrophilic polymer pervaporation membrane designed for irrigation applications were investigated. Open air experiments were conducted at room temperature for individual solutions of fluorene, naphthalene, phenol, 1,2-dichlorobenzene, 1,2-diethylbenzene and 2-phenoxyethanol. Percentage rejection generally increased with increased molecular size for the model micro-pollutants (47-86%). Molecular weight and log Kow had the strongest positive relationships with rejection, as demonstrated by respective correlation coefficients of r = 0.898 and 0.824. Rejection was also strongly negatively correlated with aqueous solubility and H-bond δ. However, properties which relate to vapour phase concentrations of the micro-pollutants were not well correlated with rejection. Thus, physicochemical separation processes, rather than vapour pressure, drive removal of aromatic contaminants by the investigated pervaporation tube. This expanded knowledge could be utilized in considering practical applications of pervaporative irrigation systems for treating organic-contaminated waters such as oilfield-produced waters.

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.

A new perspective on the apparent solubility of dissolved black carbon

NASA Astrophysics Data System (ADS)

Wagner, Sasha; Ding, Yan; Jaffé, Rudolf

2017-09-01

Black carbon (BC), pyrogenic organic matter generated from the incomplete combustion of biomass, is ubiquitous in the environment. The molecular structures which comprise the BC pool of compounds are defined by their condensed aromatic core structures polysubstituted with O-containing functionalities (e.g., carboxyl groups). Despite the apparent hydrophobicity of BC molecules, a considerable portion of BC is translocated from terrestrial to aquatic systems in the form of dissolved BC (DBC). However, the specific biogeochemical mechanisms which control the transfer of BC from the land to the water remain elusive. In the current study, the apparent solubility of DBC was inferred from octanol-water partition coefficients (Kow) modeled for proposed DBC structures with varying degrees of polycondensation and polar functionality. Modeled Kow values indicated that DBC molecules with small aromatic ring systems and high degrees of hydrophilic functionality may be truly solubilized in the aqueous phase. However, large and highly condensed DBC structures yielded high Kow values, which suggested that a considerable portion of the DBC pool which has been quantified in aquatic environments is not truly dissolved. We hypothesized that other DOM components may act as mediators in the solubilization of condensed aromatic molecules and serve to increase the solubility of DBC via hydrophobic, intermolecular associations. This hypothesis was tested through controlled leaching experiments to determine whether the mobilization of DBC from particulate soils and chars became enhanced in the presence of DOM. However, we observed that characteristics inherent to each sample type had a greater influence than added DOM on the apparent solubility of DBC. In addition, the direct comparison of molecular marker (benzenepolycarboxylic acids) and ultrahigh resolution mass spectral data (FT-ICR/MS) on leachates obtained from the same set of soils and char did not show a clear overlap in DBC quantification or characterization between the two analytical methods. Correlations between FT-ICR/MS results and BPCA were not significant possibly due to differences in the methodological windows and/or small sample size. Our results were unable to provide evidence in support of proposed hydrophobic interactions between DOM and DBC, suggesting that other physical/chemical mechanisms play important roles in the dissolution of BC.

Aqueous solubilities, vapor pressures, and 1-octanol-water partition coefficients for C9-C14 linear alkylbenzenes

USGS Publications Warehouse

Sherblom, P.M.; Gschwend, P.M.; Eganhouse, R.P.

1992-01-01

Measurements and estimates of aqueous solubilities, 1-octanol-water partition coefficients (Kow), and vapor pressures were made for 29 linear alkylbenzenes having alkyl chain lengths of 9-14 carbons. The ranges of values observed were vapor pressures from 0.002 to 0.418 Pa, log Kow, from 6.83 to 9.95, and aqueous solubilities from 4 to 38 nmol??L-1. Measured values exhibited a relationship to both the alkyl chain length and the position of phenyl substitution on the alkyl chain. Measurement of the aqueous concentrations resulting from equilibration of a mixture of alkylbenzenes yielded higher than expected values, indicating cosolute or other interactive effects caused enhanced aqueous concentrations of these compounds. ?? 1992 American Chemical Society.

RELATIONSHIPS OF QUANTITATIVE STRUCTURE-ACTIVITY TO COMPARATIVE TOXICITY OF SELECTED PHENOLS IN THE 'PIMEPHALES PROMELAS' AND 'TETRAHYMENA PYRIFORMIS' TEST SYSTEMS

EPA Science Inventory

The relative toxic response of 27 selected phenols in the 96-hr acute flowthrough Pimephales promelas (fathead minnow) and the 48- to 60-hr chronic static Tetrahymena pyriformis (ciliate protozoan) test systems was evaluated. Log Kow-dependent linear regression analyses revealed ...

Microbial Transformation of Esters of Chlorinated Carboxylic Acids

PubMed Central

Paris, D. F.; Wolfe, N. L.; Steen, W. C.

1984-01-01

Two groups of compounds were selected for microbial transformation studies. In the first group were carboxylic acid esters having a fixed aromatic moiety and an increasing length of the alkyl component. Ethyl esters of chlorine-substituted carboxylic acids were in the second group. Microorganisms from environmental waters and a pure culture of Pseudomonas putida U were used. The bacterial populations were monitored by plate counts, and disappearance of the parent compound was followed by gas-liquid chromatography as a function of time. The products of microbial hydrolysis were the respective carboxylic acids. Octanol-water partition coefficients (Kow) for the compounds were measured. These values spanned three orders of magnitude, whereas microbial transformation rate constants (kb) varied only 50-fold. The microbial rate constants of the carboxylic acid esters with a fixed aromatic moiety increased with an increasing length of alkyl substituents. The regression coefficient for the linear relationships between log kb and log Kow was high for group 1 compounds, indicating that these parameters correlated well. The regression coefficient for the linear relationships for group 2 compounds, however, was low, indicating that these parameters correlated poorly. PMID:16346459

Characteristics of trophic transfer of polychlorinated biphenyls in marine organisms in Incheon North Harbor, Korea.

PubMed

Kim, Seung Kyu; Lee, Dong Soo; Oh, Jae Ryong

2002-04-01

The trophic transfer of polychlorinated biphenyls (PCBs) was characterized for zooplankton (primarily Paracalanus spp. and Acartia spp.), pacific oyster (Crassostrea gigas), shore crab (Hemigrapsus penicillatus), and goby (Acanthogobius hasta) in the aquatic system of Incheon North Harbor, Korea. The congener pattern in the species was clearly divided by the main PCB uptake route. Compared with zooplankton and oyster, the fraction of heavier homologues increased in crab and goby that take PCBs from food. Linear relationships were observed between log (fugacity in lipid/fugacity in seawater) and log Kow for all the species. For zooplankton and oyster, such an observation should not be regarded as a true absence of superhydrophobicity, because establishment of equilibrium with seawater was not evident. For crab and goby, the absence of superhydrophobicity was evidenced by the trophic transfer factor that continuously increased with Kow up to 10(7.8). These results suggest that superhydrophobicity might be species specific. The trophic transfer factors and the fugacity levels in the lipid phase indicated that bioaccumulation in crab and goby advanced beyond the level in equilibrium with seawater in the harbor basin.

Bioaccumulation and enantioselectivity of type I and type II pyrethroid pesticides in earthworm.

PubMed

Chang, Jing; Wang, Yinghuan; Wang, Huili; Li, Jianzhong; Xu, Peng

2016-02-01

In this study, the bioavailability and enantioselectivity differences between bifenthrin (BF, typeⅠpyrethroid) and lambad-cyhalothrin (LCT, type Ⅱ pyrethroid) in earthworm (Eisenia fetida) were investigated. The bio-soil accumulation factors (BSAFs) of BF was about 4 times greater than that of LCT. LCT was degraded faster than BF in soil while eliminated lower in earthworm samples. Compound sorption plays an important role on bioavailability in earthworm, and the soil-adsorption coefficient (K(oc)) of BF and LCT were 22 442 and 42 578, respectively. Metabolic capacity of earthworm to LCT was further studied as no significant difference in the accumulation of LCT between the high and low dose experiment was found. 3-phenoxybenzoic acid (PBCOOH), a metabolite of LCT produced by earthworm was detected in soil. The concentration of PBCOOH at high dose exposure was about 4.7 times greater than that of in low dose level at the fifth day. The bioaccumulation of BF and LCT were both enantioselective in earthworm. The enantiomer factors of BF and LCT in earthworm were approximately 0.12 and 0.65, respectively. The more toxic enantiomers ((+)-BF and (-)-LCT) had a preferential degradation in earthworm and leaded to less toxicity on earthworm for racemate exposure. In combination with other studies, a liner relationship between Log BSAF(S) and Log K(ow) was observed, and the Log BSAF(S) decreased with the increase of Log K(ow). Copyright © 2015 Elsevier Ltd. All rights reserved.

Runoff of pharmaceuticals and personal care products following application of dewatered municipal biosolids to an agricultural field.

PubMed

Sabourin, Lyne; Beck, Andrew; Duenk, Peter W; Kleywegt, Sonya; Lapen, David R; Li, Hongxia; Metcalfe, Chris D; Payne, Michael; Topp, Edward

2009-08-01

Municipal biosolids are a useful source of nutrients for crop production, and commonly used in agriculture. In this field study, we applied dewatered municipal biosolids at a commercial rate using broadcast application followed by incorporation. Precipitation was simulated at 1, 3, 7, 21 and 34 days following the application on 2 m(2) microplots to evaluate surface runoff of various pharmaceuticals and personal care products (PPCPs), namely atenolol, carbamazepine, cotinine, caffeine, gemfibrozil, naproxen, ibuprofen, acetaminophen, sulfamethoxazole, triclosan and triclocarban. There was little temporal coherence in the detection of PPCPs in runoff, various compounds being detected maximally on days 1, 3, 7 or 36. Maximum concentrations in runoff ranged from below detection limit (gemfibrozil) to 109.7 ng L(-1) (triclosan). Expressing the total mass exported as a percentage of that applied, some analytes revealed little transport potential (<1% exported; triclocarban, triclosan, sulfamethoxazole, ibuprofen, naproxen and gemfibrozil) whereas others were readily exported (>1% exported; acetaminophen, carbamazepine, caffeine, cotinine, atenolol). Those compounds with little transport potential had log K(ow) values of 3.18 or greater, whereas those that were readily mobilized had K(ow) values of 2.45 or less. Maximal concentrations of all analytes were below toxic concentrations using a variety of endpoints available in the literature. In summary, this study has quantified the transport potential in surface runoff of PPCPs from land receiving biosolids, identified that log K(ow) may be a determinant of runoff transport potential of these analytes, and found maximal concentrations of all chemicals tested to be below toxic concentrations using a variety of endpoints.

A new twist on an old regression: transfer of chemicals to beef and milk in human and ecological risk assessment.

PubMed

Hendriks, A Jan; Smítková, Hana; Huijbregts, Mark A J

2007-11-01

Exposure of humans to chemicals in beef or milk is part of almost all risk evaluation procedures carried out to reduce emissions or to remediate sites. Concentrations of substances in these livestock products are often estimated using log-log regressions that relate the biotransfer factor BTF to the octanol-water partition ratio K(ow). However, the correctness of these empirical correlations has been questioned. Here, we compare them to the mechanistic model OMEGA that describes the distribution of substances in organisms by integrating theory on chemical fugacity and biological allometry. OMEGA has been calibrated and validated on thousands of laboratory and field data, reflecting many chemical substances and biological species. Overall fluxes of water, food, tissue (growth), milk and stable substances calculated by OMEGA are within a factor of two from independent data obtained in experiments. Rate constants measured for elimination of individual compounds of a recalcitrant nature vary around the level expected from the model for output to faeces and milk. Both data and model suggest that biotransfer BTF of stable substances to beef and milk is independent of the octanol-water partition ratio K(ow) in the range of 10(3)-10(6). This contradicts empirical regressions including stable and labile compounds. As expected, levels of labile substances vary widely around a tentative indication derived from the model. Transformation and accumulation of labile substances remains highly specific for the chemical and organism concerned but depends weakly on the octanol-water partition ratio K(ow). Several possibilities for additional refinement are identified.

Advances in understanding the response of fish to linear alcohols in the environment.

PubMed

Belanger, Scott E; Rawlings, Jane M; Stackhouse, Ricky

2018-09-01

Short to long chain alcohols have a range of ecotoxicity to aquatic life driven by hydrophobic interactions with biological membranes. Carbon chain length and octanol:water partitioning coefficients are surrogates for hydrophobicity and strongly relate to aquatic toxicity. In these investigations, the toxicity of ethanol to 1-n-dodecanol to juvenile fish in standard acute toxicity tests is reviewed. Toxicity tests employing fish embryos (zebrafish Danio rerio and fathead minnow Pimephales promelas) in the Fish Embryo Test (OECD 236) format were conducted from C2 to C10 to compare against standard juvenile fish toxicity. Quantitative structure activity relationships for FET and fish individually and combined demonstrate that embryos are not different in sensitivity to juvenile fish. A combined QSAR was developed of the form Log 96 h LC50 (mM/L) = -0.925*log Kow + 2.060 (R2 10 = 0.954). Alcohols of 11-12 carbons show a deflection in the QSAR as toxicity approaches the solubility limit. Alcohols with longer chain lengths may only be tested at lower exposures relevant for chronic toxicity. Decanol was evaluated in a 33-d fish early life stage test (OECD 210) and survival was the most sensitive endpoint (EC10 = 0.43 mg/L, 0.0027 mM/L). This study suggests a reasonable acute to chronic ratio of 6.5 in line with historical literature for non-polar narcotic compounds. Fish are not uniquely more sensitive than Daphnia magna which suggests estimations of environmental hazard can be confidently made with either taxon. The overall environmental risk assessments for the longer chain alcohols included in this research remain largely unchanged primarily due to previous research demonstrating a very minimal environmental exposure even for highly toxic members of the category. Copyright © 2018 Elsevier Ltd. All rights reserved.

Effect of drug lipophilicity on in vitro release rate from oil vehicles using nicotinic acid esters as model prodrug derivatives.

PubMed

Weng Larsen, S; Engelbrecht Thomsen, A E; Rinvar, E; Friis, G J; Larsen, C

2001-03-23

The rate constants for transfer of a homologous series of nicotinic acid esters from oil vehicles to aqueous buffer phases were determined using a rotating dialysis cell. The chemical stability of butyl nicotinate has been investigated at 60 degrees C over pH range 0.5--10. Maximum stability occurs at pH 4--5 and an inflection point was seen around the pK(a). For the nicotinic acid esters, a linear correlation was established between the first-order rate constant related to attainment of equilibrium, k(obs) and the apparent partition coefficient, P(app): log k(obs)=-0.83log P(app)+0.26 (k(obs) in h(-1), n=9). For hexyl nicotinate with a true partition coefficient of 4 it was possible to determine k(obs) by decreasing pH in the aqueous release medium to 2.05. Thus, under the latter experimental conditions estimation of the relative release rates for the esters were performed. The ratio between the specific rate constant k(ow), related to the transport from oil vehicle to aqueous phase, for ethyl and hexyl nicotinate was 139. The hydrophobic substituent constant for a methylene group, pi(CH(2)), was determined for nicotinic acid esters in different oil/buffer partitioning systems to 0.54--0.58. Addition of hydroxypropyl-beta-cyclodextrin to the aqueous release medium did not enhance the transport rate of the esters from the oil phase.

Thiol reactivity and its impact on the ciliate toxicity of α,β-unsaturated aldehydes, ketones, and esters.

PubMed

Böhme, Alexander; Thaens, Diana; Schramm, Franziska; Paschke, Albrecht; Schüürmann, Gerrit

2010-12-20

A recently introduced chemoassay has been used to determine second-order rate constants of the electrophile-nucleophile reaction of 15 α,β-unsaturated aldehydes with glutathione. The respective kGSH values vary for more than 3 orders of magnitude, and are within the range determined previously for 31 α,β-unsaturated ketones and esters. Structure-reactivity analyses yield distinct relationships between kGSH and structural features of the compounds. Moreover, increasing kGSH increases the aldehyde toxicity toward ciliates in terms of 48 h-EC50 values (effective concentration yielding 50% growth inhibition of Tetrahymena pyriformis within 48 h). A respective log-log regression equation including both kGSH and the octanol/water partition coefficient, Kow, yields a squared correlation coefficient of 0.96. Comparative analysis with corresponding data for 15 ketones and 16 esters reveals systematic differences between the three compound classes with regard to the individual contributions of hydrophobicity and electrophilic reactivity to aquatic toxicity. The former is particularly pronounced for aldehydes, while the ester toxicity is largely governed by reactivity, with ketones showing an intermediate pattern that is more similar to the one of esters than of aldehydes. It follows that within the Michael acceptor domain of α,β-unsaturated carbonyls, a distinction between aldehydes and nonaldehydic derivatives appears necessary when employing electrophilic reactivity as a component for the quantitative prediction of their reactive toxicity toward aquatic organisms.

Determination of polyparameter linear free energy relationship (pp-LFER) substance descriptors for established and alternative flame retardants.

PubMed

Stenzel, Angelika; Goss, Kai-Uwe; Endo, Satoshi

2013-02-05

Polyparameter linear free energy relationships (pp-LFERs) can predict partition coefficients for a multitude of environmental and biological phases with high accuracy. In this work, the pp-LFER substance descriptors of 40 established and alternative flame retardants (e.g., polybrominated diphenyl ethers, hexabromocyclododecane, bromobenzenes, trialkyl phosphates) were determined experimentally. In total, 251 data for gas-chromatographic (GC) retention times and liquid/liquid partition coefficients (K) were measured and used to calibrate the pp-LFER substance descriptors. Substance descriptors were validated through a comparison between predicted and experimental log K for the systems octanol/water (K(ow)), water/air (K(wa)), organic carbon/water (K(oc)) and liposome/water (K(lipw)), revealing a high reliability of pp-LFER predictions based on our descriptors. For instance, the difference between predicted and experimental log K(ow) was <0.3 log units for 17 out of 21 compounds for which experimental values were available. Moreover, we found an indication that the H-bond acceptor value (B) depends on the solvent for some compounds. Thus, for predicting environmentally relevant partition coefficients it is important to determine B values using measurements in aqueous systems. The pp-LFER descriptors calibrated in this study can be used to predict partition coefficients for which experimental data are unavailable, and the predicted values can serve as references for further experimental measurements.

Dermal uptake and percutaneous penetration of ten flame retardants in a human skin ex vivo model.

PubMed

Frederiksen, Marie; Vorkamp, Katrin; Jensen, Niels Martin; Sørensen, Jens Ahm; Knudsen, Lisbeth E; Sørensen, Lars S; Webster, Thomas F; Nielsen, Jesper B

2016-11-01

The dermal uptake and percutaneous penetration of ten organic flame retardants was measured using an ex vivo human skin model. The studied compounds were DBDPE, BTBPE, TBP-DBPE, EH-TBB, BEH-TEBP, α, β and γ-HBCDD as well as syn- and anti-DDC-CO. Little or none of the applied flame retardants was recovered in either type of the receptor fluids used (physiological and worst-case). However, significant fractions were recovered in the skin depot, particularly in the upper skin layers. The primary effect of the worst-case receptor fluid was deeper penetration into the skin. The recovered mass was used to calculate lower- and upper-bound permeability coefficients kp. Despite large structural variation between the studied compounds, a clear, significant decreasing trend of kp was observed with increasing log Kow. The results indicate that the dermis may provide a significant barrier for these highly lipophilic compounds. However, based on our results, dermal uptake should be considered in exposure assessments, though it may proceed in a time-lagged manner compared to less hydrophobic compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

Adsorptive removal of pharmaceuticals from water by commercial and waste-based carbons.

PubMed

Calisto, Vânia; Ferreira, Catarina I A; Oliveira, João A B P; Otero, Marta; Esteves, Valdemar I

2015-04-01

This work describes the single adsorption of seven pharmaceuticals (carbamazepine, oxazepam, sulfamethoxazole, piroxicam, cetirizine, venlafaxine and paroxetine) from water onto a commercially available activated carbon and a non-activated carbon produced by pyrolysis of primary paper mill sludge. Kinetics and equilibrium adsorption studies were performed using a batch experimental approach. For all pharmaceuticals, both carbons presented fast kinetics (equilibrium times varying from less than 5 min to 120 min), mainly described by a pseudo-second order model. Equilibrium data were appropriately described by the Langmuir and Freundlich isotherm models, the last one giving slightly higher correlation coefficients. The fitted parameters obtained for both models were quite different for the seven pharmaceuticals under study. In order to evaluate the influence of water solubility, log Kow, pKa, polar surface area and number of hydrogen bond acceptors of pharmaceuticals on the adsorption parameters, multiple linear regression analysis was performed. The variability is mainly due to log Kow followed by water solubility, in the case of the waste-based carbon, and due to water solubility in the case of the commercial activated carbon. Copyright © 2015 Elsevier Ltd. All rights reserved.

Fate and movement of azaarenes and their anaerobic biotransformation products in an aquifer contaminated by wood-treatment chemicals

USGS Publications Warehouse

Pereira, W.E.; Rostad, C.E.; Updegraff, D.M.; Bennett, J.L.

1987-01-01

Infiltration of wastes containing creosote and pentachlorophenol from surface impoundments at an abandoned wood-treatment facility near Pensacola, Florida, resulted in contamination of the underlying sand and gravel aquifer. Pond sludges and sediments near the source were contaminated with 2- to 5-ring azaarenes having log Kow values of from 2.0 to 5.6. However, the ground water contained only azaarenes and their oxygenated and methylated derivatives having log Kow values of less than 3.5. These compounds also were present in coal tar-contaminated ground water at a site near St. Louis Park, Minnesota. Laboratory anaerobic degradation studies and on-site observations indicated that oxygenated azaarenes probably were biotransformation products of reactions mediated by indigenous microbial populations. Microbial N-methylation, C-methylation and O-methylation reactions are reported here for the first time. In the presence of nutrients and carbon sources such as acetate and propionate, all azaarenes studied were either partially or completely degraded. Evidence for the microbial degradation of azaarenes in ground water from anaerobic zones is presented. Oxygenated azaarenes were relatively more water-soluble, mobile and persistent in hydrogeologic environments. ?? 1987.

Transfer rates of 19 typical pesticides and the relationship with their physicochemical property.

PubMed

Chen, Hongping; Pan, Meiling; Pan, Rong; Zhang, Minglu; Liu, Xin; Lu, Chengyin

2015-01-21

Determining the transfer rate of pesticides during tea brewing is important to identify the potential exposure risks from pesticide residues in tea. In this study, the transfer rates of 19 typical pesticides from tea to brewing were investigated using gas chromatography tandem mass and ultraperformance liquid chromatography tandem mass. The leaching rates of five pesticides (isocarbophos, triazophos, fenvalerate, buprofezin, and pyridaben) during tea brewing were first reported. The pesticides exhibited different transfer rates; however, this result was not related to residual concentrations and tea types. Pesticides with low octanol-water partition coefficients (Logkow) and high water solubility demonstrated high transfer rates. The transfer rates of pesticides with water solubility > 29 mg L(-1) (or <15 mg L(-1)) were >25% (or <10%), and those of pesticides with LogKow < 1.52 (or >2.48) were >65% (or <35%). This result indicates that water solubility at approximately 20 mg L(-1) and LogKow at approximately 2.0 could be the demarcation lines of transfer rate. The results of this study can be used as a guide in the application of pesticides to tea trees and establishment of maximum residue limits of pesticides in tea to reduce pesticide exposure in humans.

Chromatographic retention prediction and octanol-water partition coefficient determination of monobasic weak acidic compounds in ion-suppression reversed-phase liquid chromatography using acids as ion-suppressors.

PubMed

Ming, Xin; Han, Shu-ying; Qi, Zheng-chun; Sheng, Dong; Lian, Hong-zhen

2009-08-15

Although simple acids, replacing buffers, have been widely applied to suppress the ionization of weakly ionizable acidic analytes in reversed-phase liquid chromatography (RPLC), none of the previously reported works focused on the systematic studies about the retention behavior of the acidic solutes in this ion-suppression RPLC mode. The subject of this paper was therefore to investigate the retention behavior of monobasic weak acidic compounds using acetic, perchloric and phosphoric acids as the ion-suppressors. The apparent octanol-water partition coefficient (K" ow) was proposed to calibrate the octanol-water partition coefficient (K(ow)) of these weak acidic compounds, which resulted in a better linear correlation with log k(w), the logarithm of the hypothetical retention factor corresponding to neat aqueous fraction of hydroorganic mobile phase. This log K" ow-log k w linear correlation was successfully validated by the results of monocarboxylic acids and monohydrating phenols, and moreover by the results under diverse experimental conditions for the same solutes. This straightforward relationship not only can be used to effectively predict the retention values of weak acidic solutes combined with Snyder-Soczewinski equation, but also can offer a promising medium for directly measuring K(ow) data of these compounds via Collander equation. In addition, the influence of the different ion-suppressors on the retention of weak acidic compounds was also compared in this RPLC mode.

Persistent organic pollutants in British Columbia grizzly bears: consequence of divergent diets.

PubMed

Christensen, Jennie R; MacDuffee, Misty; Macdonald, Robie W; Whiticar, Michael; Ross, Peter S

2005-09-15

Nitrogen and carbon stable isotope signatures in growing hair reveal that while some British Columbia grizzly bears (Ursus arctos horribilis) rely entirely on terrestrial foods, others switch in late summer to returning Pacific salmon (Oncorynchus spp.). Implications for persistent organic pollutant (POP) concentrations and patterns measured in the two feeding groups of grizzly bears were profound. While the bears consuming a higher proportion of terrestrial vegetation ("interior" grizzlies) exhibited POP patterns dominated bythe more volatile organochlorine (OC) pesticides and the heavier polybrominated diphenyl ethers (PBDEs: e.g., BDE-209), the bears consuming salmon were dominated by the more bioaccumulative POPs (e.g., DDT, chlordanes, and BDE-47). The ocean-salmon-bear pathway appeared to preferentially select for those contaminants with intermediate partitioning strength from water into lipid (log Kow approximately 6.5). This pattern reflects an optimum contaminant log Kow range for atmospheric transport, deposition into the marine environment, uptake into marine biota, accumulation through the food web, and retention in the bear tissues. We estimate that salmon deliver 70% of all OC pesticides, up to 85% of the lower brominated PBDE congeners, and 90% of PCBs found in salmon-eating grizzly bears, thereby inextricably linking these terrestrial predators to contaminants from the North Pacific Ocean.

Application of PAH concentration profiles in lake sediments as indicators for smelting activity.

PubMed

Warner, Wiebke; Ruppert, Hans; Licha, Tobias

2016-09-01

The ability of lake sediment cores to store long-term anthropogenic pollution establishes them as natural archives. In this study, we focus on the influence of copper shale mining and smelting in the Mansfeld area of Germany, using the depth profiles of two sediment cores from Lake Süßer See. The sediment cores provide a detailed chronological deposition history of polycyclic aromatic hydrocarbons (PAHs) and heavy metals in the studied area. Theisen sludge, a fine-grained residue from copper shale smelting, reaches the lake via deflation by wind or through riverine input; it is assumed to be the main source of pollution. To achieve the comparability of absolute contaminant concentrations, we calculated the influx of contaminants based on the sedimentation rate. Compared to the natural background concentrations, PAHs are significantly more enriched than heavy metals. They are therefore more sensitive and selective for source apportionment. We suggest two diagnostic ratios of PAHs to distinguish between Theisen sludge and its leachate: the ratio fluoranthene to pyrene ~2 and the ratio of PAH with logKOW<5.7 to PAH with a logKOW>5.7 converging to an even lower value than 2.3 (the characteristic of Theisen sludge) to identify the particulate input in lake environments. Copyright © 2016 Elsevier B.V. All rights reserved.

Quantitative structure-property relationships for octanol-water partition coefficients of polybrominated diphenyl ethers.

PubMed

Li, Linnan; Xie, Shaodong; Cai, Hao; Bai, Xuetao; Xue, Zhao

2008-08-01

Theoretical molecular descriptors were tested against logK(OW) values for polybrominated diphenyl ethers (PBDEs) using the Partial Least-Squares Regression method which can be used to analyze data with many variables and few observations. A quantitative structure-property relationship (QSPR) model was successfully developed with a high cross-validated value (Q(cum)(2)) of 0.961, indicating a good predictive ability and stability of the model. The predictive power of the QSPR model was further cross-validated. The values of logK(OW) for PBDEs are mainly governed by molecular surface area, energy of the lowest unoccupied molecular orbital and the net atomic charges on the oxygen atom. All these descriptors have been discussed to interpret the partitioning mechanism of PBDE chemicals. The bulk property of the molecules represented by molecular surface area is the leading factor, and K(OW) values increase with the increase of molecular surface area. Higher energy of the lowest unoccupied molecular orbital and higher net atomic charge on the oxygen atom of PBDEs result in smaller K(OW). The energy of the lowest unoccupied molecular orbital and the net atomic charge on PBDEs oxygen also play important roles in affecting the partition of PBDEs between octanol and water by influencing the interactions between PBDEs and solvent molecules.

A novel evaluation method for extrapolated retention factor in determination of n-octanol/water partition coefficient of halogenated organic pollutants by reversed-phase high performance liquid chromatography.

PubMed

Han, Shu-ying; Liang, Chao; Qiao, Jun-qin; Lian, Hong-zhen; Ge, Xin; Chen, Hong-yuan

2012-02-03

The retention factor corresponding to pure water in reversed-phase high performance liquid chromatography (RP-HPLC), k(w), was commonly obtained by extrapolation of retention factor (k) in a mixture of organic modifier and water as mobile phase in tedious experiments. In this paper, a relationship between logk(w) and logk for directly determining k(w) has been proposed for the first time. With a satisfactory validation, the approach was confirmed to enable easy and accurate evaluation of k(w) for compounds in question with similar structure to model compounds. Eight PCB congeners with different degree of chlorination were selected as a training set for modeling the logk(w)-logk correlation on both silica-based C(8) and C(18) stationary phases to evaluate logk(w) of sample compounds including seven PCB, six PBB and eight PBDE congeners. These eight model PCBs were subsequently combined with seven structure-similar benzene derivatives possessing reliable experimental K(ow) values as a whole training set for logK(ow)-logk(w) regressions on the two stationary phases. Consequently, the evaluated logk(w) values of sample compounds were used to determine their logK(ow) by the derived logK(ow)-logk(w) models. The logK(ow) values obtained by these evaluated logk(w) were well comparable with those obtained by experimental-extrapolated logk(w), demonstrating that the proposed method for logk(w) evaluation in this present study could be an effective means in lipophilicity study of environmental contaminants with numerous congeners. As a result, logK(ow) data of many PCBs, PBBs and PBDEs could be offered. These contaminants are considered to widely exist in the environment, but there have been no reliable experimental K(ow) data available yet. Copyright © 2011 Elsevier B.V. All rights reserved.

Pharmaceutical removal in tropical subsurface flow constructed wetlands at varying hydraulic loading rates.

PubMed

Zhang, Dong Qing; Gersberg, Richard M; Hua, Tao; Zhu, Junfei; Tuan, Nguyen Anh; Tan, Soon Keat

2012-04-01

Determining the fate of emerging organic contaminants in an aquatic ecosystem is important for developing constructed wetlands (CWs) treatment technology. Experiments were carried out in subsurface flow CWs in Singapore to evaluate the fate and transport of eight pharmaceutical compounds. The CW system included three parallel horizontal subsurface flow CWs and three parallel unplanted beds fed continuously with synthetic wastewater at different hydraulic retention times (HRTs). The findings of the tests at 2-6 d HRTs showed that the pharmaceuticals could be categorized as (i) efficiently removed compounds with removal higher than 85% (ketoprofen and salicylic acid); (ii) moderately removed compounds with removal efficiencies between 50% and 85% (naproxen, ibuprofen and caffeine); and (iii) poorly removed compounds with efficiency rate lower than 50% (carbamazepine, diclofenac, and clofibric acid). Except for carbamazepine and salicylic acid, removal efficiencies of the selected pharmaceuticals showed significant (p<0.05) enhancement in planted beds as compared to the unplanted beds. Removal of caffeine, ketoprofen and clofibric acid were found to follow first order decay kinetics with decay constants higher in the planted beds than the unplanted beds. Correlations between pharmaceutical removal efficiencies and log K(ow) were not significant (p>0.05), implying that their removal is not well related to the compound's hydrophobicity. Copyright © 2011 Elsevier Ltd. All rights reserved.

Assessing Aromatic-Hydrocarbon Toxicity to Fish Early Life Stages Using Passive-Dosing Methods and Target-Lipid and Chemical-Activity Models.

PubMed

Butler, Josh D; Parkerton, Thomas F; Redman, Aaron D; Letinski, Daniel J; Cooper, Keith R

2016-08-02

Aromatic hydrocarbons (AH) are known to impair fish early life stages (ELS). However, poorly defined exposures often confound ELS-test interpretation. Passive dosing (PD) overcomes these challenges by delivering consistent, controlled exposures. The objectives of this study were to apply PD to obtain 5 d acute embryo lethality and developmental data and 30 d chronic embryo-larval survival and growth-effects data using zebrafish with different AHs; to analyze study and literature toxicity data using target-lipid (TLM) and chemical-activity (CA) models; and to extend PD to a mixture and test the assumption of AH additivity. PD maintained targeted exposures over a concentration range of 6 orders of magnitude. AH toxicity increased with log Kow up to pyrene (5.2). Pericardial edema was the most sensitive sublethal effect that often preceded embryo mortality, although some AHs did not produce developmental effects at concentrations causing mortality. Cumulative embryo-larval mortality was more sensitive than larval growth, with acute-to-chronic ratios of <10. More-hydrophobic AHs did not exhibit toxicity at aqueous saturation. The relationship and utility of the TLM-CA models for characterizing fish ELS toxicity is discussed. Application of these models indicated that concentration addition provided a conservative basis for predicting ELS effects for the mixture investigated.

Coupling passive sampling with in vitro bioassays and chemical analysis to understand combined effects of bioaccumulative chemicals in blood of marine turtles.

PubMed

Jin, Ling; Escher, Beate I; Limpus, Colin J; Gaus, Caroline

2015-11-01

Conventional target analysis of biological samples such as blood limits our ability to understand mixture effects of chemicals. This study aimed to establish a rapid passive sampling technique using the polymer polydimethylsiloxane (PDMS) for exhaustive extraction of mixtures of neutral organic chemicals accumulated in blood of green turtles, in preparation for screening in in vitro bioassays. We designed a PDMS-blood partitioning system based on the partition coefficients of chemicals between PDMS and major blood components. The sampling kinetics of hydrophobic test chemicals (polychlorinated dibenzo-p-dioxins; PCDDs) from blood into PDMS were reasonably fast reaching steady state in <96 h. The geometric mean of the measured PDMS-blood partition coefficients for PCDDs, polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) was 14 L blood kg PDMS(-1) and showed little variability (95% confidence interval from 8.4 to 29) across a wide range of hydrophobicity (logKow 5.7-8.3). The mass transfer of these chemicals from 5 mL blood into 0.94 g PDMS was 62-84%, which is similar to analytical recoveries in conventional solvent extraction methods. The validated method was applied to 15 blood samples from green turtles with known concentrations of PCDD/Fs, dioxin-like PCBs, PBDEs and organochlorine pesticides. The quantified chemicals explained most of the dioxin-like activity (69-98%), but less than 0.4% of the oxidative stress response. The results demonstrate the applicability of PDMS-based passive sampling to extract bioaccumulative chemicals from blood as well as the value of in vitro bioassays for capturing the combined effects of unknown and known chemicals. Copyright © 2015 Elsevier Ltd. All rights reserved.

New insights into the interactions between cork chemical components and pesticides. The contribution of π-π interactions, hydrogen bonding and hydrophobic effect.

PubMed

Olivella, M À; Bazzicalupi, C; Bianchi, A; Fiol, N; Villaescusa, I

2015-01-01

The role of chemical components of cork in the sorption of several pesticides has been investigated. For this purpose raw cork and three cork extracted fractions (i.e. cork free of aliphatic extractives, cork free of all extractives and cork free of all extractives and suberin) were used as sorbent of three ionic pesticides (propazine, 2,4-dichlorophenoxy acetic acid (2,4-D) and alachlor) and five non-ionic pesticides (chlorpyrifos, isoproturon, metamitron, methomyl and oxamyl) with a logKow within the range -0.47 to 4.92. The effect of cations on the ionic pesticides, propazine and 2,4-D sorption was also analyzed. Results indicated that the highest yields were obtained for chlorpyrifos and alachlor sorption onto raw cork (>55%). After removal of aliphatic extractives sorption of all pesticides increased that ranged from 3% for propazine to 31% for alachlor. In contrast, removal of phenolic extractives caused a sorption decrease. Low sorption yields were obtained for hydrophobic pesticides such as metamitron, oxamyl and methomyl (<11%) by using all cork fractions and extremely low when using raw cork (<1%). FTIR analysis was useful to indicate that lignin moieties were the main components involved on the sorption process. Modelling calculations evidenced that π-stacking interactions with the aromatic groups of lignin play a major role in determining the adsorption properties of cork toward aromatic pesticides. Results presented in this paper gain insights into the cork affinities for pesticides and the interactions involved in the sorption process and also enables to envisage sorption affinity of cork for other organic pollutants. Copyright © 2014 Elsevier Ltd. All rights reserved.

[Adsorption of phenol chemicals by surfactant-modified zeolites].

PubMed

Xie, Jie; Wang, Zhe; Wu, De-Yi; Li, Chun-Jie

2012-12-01

Two kinds of zeolites were prepared from fly ash and modified by surfactant subsequently. Surfactant-modified zeolites were studied for adsorption of phenol chemicals (phenol, p-chlorphenol, bisphenol A). It showed that the adsorption affinity of zeolite to phenol chemicals was significantly improved after surfactant modification. The adsorption isotherms of phenol chemicals were well fitted by the Langmuir isotherm. For the two surfactant-surfactant modified zeolites, the maximum adsorption amounts of phenol, p-chlorphenol, and bisphenol A calculated from the Langmuir equation were 37.7, 52.36, 90.9 mg x g(-1) and 10.7, 22.83, 56.8 mg x g(-1), respectively. When pH values of solutions were higher than the pK(a) values of phenol chemicals, the removal efficiencies were getting higher with the increase of pH values. The octanol/water partition coefficient (K(ow)) was also found to be an important factor affecting adsorption of phenol chemicals by the modified zeolites. Higher K(ow) value, which means the greater hydrophobicity of the chemicals, resulted in a higher removal.

Three-parameter modeling of the soil sorption of acetanilide and triazine herbicide derivatives.

PubMed

Freitas, Mirlaine R; Matias, Stella V B G; Macedo, Renato L G; Freitas, Matheus P; Venturin, Nelson

2014-02-01

Herbicides have widely variable toxicity and many of them are persistent soil contaminants. Acetanilide and triazine family of herbicides have widespread use, but increasing interest for the development of new herbicides has been rising to increase their effectiveness and to diminish environmental hazard. The environmental risk of new herbicides can be accessed by estimating their soil sorption (logKoc), which is usually correlated to the octanol/water partition coefficient (logKow). However, earlier findings have shown that this correlation is not valid for some acetanilide and triazine herbicides. Thus, easily accessible quantitative structure-property relationship models are required to predict logKoc of analogues of the these compounds. Octanol/water partition coefficient, molecular weight and volume were calculated and then regressed against logKoc for two series of acetanilide and triazine herbicides using multiple linear regression, resulting in predictive and validated models.

Partitioning and bioaccumulation of PCBs and PBDEs in marine plankton from the Strait of Georgia, British Columbia, Canada

NASA Astrophysics Data System (ADS)

Frouin, Heloise; Dangerfield, Neil; Macdonald, Robie W.; Galbraith, M.; Crewe, Norman; Shaw, Patrick; Mackas, David; Ross, Peter S.

2013-08-01

The Strait of Georgia is a large, deep, fjord-like estuary on the southern coast of British Columbia which is subject to local and atmospheric inputs of persistent environmental contaminants. We measured 204 polychlorinated biphenyls (PCBs) and 61 polybrominated diphenyl ethers (PBDEs) seasonally in water (two depths; dissolved and particle-bound) and plankton (vertical tow) samples collected at two stations. Principal components analysis clearly distinguished the dissolved and particulate water fractions and plankton samples, with the latter two compartments associated more with heavier congeners. Bioaccumulation factors (log BAFs) for PCBs and PBDEs in plankton were best described by parabolic relationships against octanol-water partitioning coefficients (log Kow), peaking at a log Kow of 5-7, underscoring the important role of physico-chemical properties in driving the uptake of these persistent contaminants by plankton from water. The estimated total quantity of PCBs (annual average of 0.61 ± SEM 0.12 kg) and PBDEs (annual average of 0.64 ± 0.19 kg) in Strait of Georgia plankton biomass were remarkably similar, highlighting the emergence of currently-used PBDEs as a priority concern. The estimated total of 52.1 ± 8.41 kg of PCBs in water (dissolved + particle-bound) was higher than the estimated 26.8 ± 5.20 kg of PBDEs (dissolved + particle-bound), reflecting the dichotomous use histories for these two contaminant classes. Results provide insight into the biological availability of PCBs and PBDEs to the Strait of Georgia food web, and describe an important initial partitioning process by which the region's endangered killer whales have become highly contaminated.

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.

Contamination of estuarine water, biota, and sediment by halogenated organic compounds: A field study

USGS Publications Warehouse

Pereira, W.E.; Rostad, C.E.; Chiou, C.T.; Brinton, T.I.; Barber, L.B.; Demcheck, D.K.; Demas, C.R.

1988-01-01

Studies conducted in the vicinity of an industrial outfall in the Calcasieu River estuary, Louisiana, have shown that water, bottom and suspended sediment, and four different species of biota are contaminated with halogenated organic compounds (HOC) including haloarenes. A "salting-out" effect in the estuary moderately enhanced the partitioning tendency of the contaminants into biota and sediments. Contaminant concentrations in water, suspended sediments, and biota were found to be far below the values predicted on the basis of the assumption of phase equilibria with respect to concentrations in bottom sediment. Relative concentration factors of HOC between biota (catfish) and bottom sediment increased with increasing octanol/estuarine water partition coefficients (Kow*), maximizing at log Kow* of about 5, although these ratios were considerably less than equilibrium values. In contrast, contaminant concentrations in water, biota, and suspended sediments were much closer to equilibrium values. Bioconcentration factors of HOC determined on the basis of lipid content for four different biotic species correlated reasonably well with equilibrium triolein/water partition coefficients (Ktw).

Pesticide contamination of Tenebrio molitor (Coleoptera: Tenebrionidae) for human consumption.

PubMed

Houbraken, Michael; Spranghers, Thomas; De Clercq, Patrick; Cooreman-Algoed, Margot; Couchement, Tasmien; De Clercq, Griet; Verbeke, Sarah; Spanoghe, Pieter

2016-06-15

The use of pesticides contributes to the productivity and the quality of the cultivated crop. A large portion of the agricultural produce is not consumed as it is not an edible part or the quality of the product is too low. This waste of agricultural produce can be valorised as a substrate for the production of certain insects for human consumption. However, pesticides applied on the plants might accumulate during the life cycle of the insects fed on the waste materials and may cause a health risk to humans consuming the insects. Pesticide residues in larvae of the yellow mealworm, Tenebrio molitor, were investigated. We monitored the accumulation of pesticides in the larvae upon consumption of contaminated fresh produce. An increased uptake rate by the insects was found for pesticides with higher Kow-values. Excretion of pesticides by the insect was inversely related to the log(Kow) values of the pesticides. Copyright © 2016 Elsevier Ltd. All rights reserved.

Silicone rubber selection for passive sampling of pesticides in water.

PubMed

Martin, A; Margoum, C; Randon, J; Coquery, M

2016-11-01

Silicone rubber can extract organic compounds with a broad range of polarities (logKow>2-3) from aqueous samples. Such compounds include substances of major concern in the protection of aquatic ecosystems and human health, e.g. pesticides. Silicone rubbers (SRs) with various characteristics have been successfully used in sorptive methods for water sample extraction in the laboratory (SPME, SBSE), and for passive sampling in aquatic environments. However, only few studies have evaluated variability in organic compound sorption due to the origin of SRs, particularly for pesticides. The aim of this study was to select an SR for the extraction of pesticides from water samples by passive sampling. To this end we measured the impact of seven SR formulations on sorption capacity, defined by the partition coefficient (Ksw). Kinetic experiments and sorption isotherms were performed to determine extraction recovery as a selection criterion for SRs, and pesticide partition coefficients. Very large differences in affinity for pesticides were found between two kinds of SRs: "Polymerized SR kits" and "Manufactured SRs". One SR was chosen among the "Manufactured SRs", and the Ksw values of 21 pesticides were determined, filling a gap in the literature (1.50

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.

Adsorption of hydrophobic organic compounds onto a hydrophobic carbonaceous geosorbent in the presence of surfactants.

PubMed

Wang, Peng; Keller, Arturo A

2008-06-01

The adsorption of hydrophobic organic compounds (HOCs; atrazine and diuron) onto lampblack was studied in the presence of nonionic, cationic, and anionic surfactants (Triton(R) X-100), benzalkonium chloride [BC], and linear alkylbenzene sulfonate [LAS]) to determine the effect of the surfactant on HOC adsorption onto a hydrophobic carbonaceous geosorbent. Linear alkylbenzene sulfonate showed an adsorption capacity higher than that of BC but similar to that of Triton X-100, implying the charge property of a surfactant is not a useful indicator for predicting the surfactant's adsorption onto a hydrophobic medium. The results also indicated that the octanol-water partition coefficient (K(OW)) of a surfactant is not a good predictor of that surfactant's sorption onto a hydrophobic medium. Under subsaturation adsorption conditions (i.e., before sorption saturation is reached), surfactant adsorption reduced HOC adsorption to a significant extent, with the reduction in HOC adsorption increasing monotonically with the amount of surfactant adsorbed. Among the three surfactants, Triton X-100 was the most effective in reducing HOC adsorption, whereas BC and LAS showed similar effectiveness in this regard. Under the same amount of the surfactant sorbed, the reduction in atrazine adsorption was consistently greater than that for diuron because of atrazine's lower hydrophobicity. No significant difference was observed in the amount of the HOC adsorbed under different adsorption sequences. Our results showed that the presence of surfactant can significantly decrease HOC adsorption onto hydrophobic environmental media and, thus, is important in predicting HOC fate and transport in the environment.

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

Removal of polycyclic aromatic hydrocarbons from aqueous solution by raw and modified plant residue materials as biosorbents.

PubMed

Xi, Zemin; Chen, Baoliang

2014-04-01

Removal of polycyclic aromatic hydrocarbons (PAHs), e.g., naphthalene, acenaphthene, phenanthrene and pyrene, from aqueous solution by raw and modified plant residues was investigated to develop low cost biosorbents for organic pollutant abatement. Bamboo wood, pine wood, pine needles and pine bark were selected as plant residues, and acid hydrolysis was used as an easily modification method. The raw and modified biosorbents were characterized by elemental analysis, Fourier transform infrared spectroscopy and scanning electron microscopy. The sorption isotherms of PAHs to raw biosorbents were apparently linear, and were dominated by a partitioning process. In comparison, the isotherms of the hydrolyzed biosorbents displayed nonlinearity, which was controlled by partitioning and the specific interaction mechanism. The sorption kinetic curves of PAHs to the raw and modified plant residues fit well with the pseudo second-order kinetics model. The sorption rates were faster for the raw biosorbents than the corresponding hydrolyzed biosorbents, which was attributed to the latter having more condensed domains (i.e., exposed aromatic core). By the consumption of the amorphous cellulose component under acid hydrolysis, the sorption capability of the hydrolyzed biosorbents was notably enhanced, i.e., 6-18 fold for phenanthrene, 6-8 fold for naphthalene and pyrene and 5-8 fold for acenaphthene. The sorption coefficients (Kd) were negatively correlated with the polarity index [(O+N)/C], and positively correlated with the aromaticity of the biosorbents. For a given biosorbent, a positive linear correlation between logKoc and logKow for different PAHs was observed. Interestingly, the linear plots of logKoc-logKow were parallel for different biosorbents. These observations suggest that the raw and modified plant residues have great potential as biosorbents to remove PAHs from wastewater. Copyright © 2014 The Research Centre for Eco-Environmental Sciences, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

Evaluation of the phase ratio for three C18 high performance liquid chromatographic columns.

PubMed

Caiali, Edvin; David, Victor; Aboul-Enein, Hassan Y; Moldoveanu, Serban C

2016-02-26

For a chromatographic column, phase ratio Φ is defined as the ratio between the volume of the stationary phase Vst and the void volume of the column V0, and it is an important parameter characterizing the HPLC process. Although apparently simple, the evaluation of Φ presents difficulties because there is no sharp boundary between the mobile phase and the stationary phase. In addition, the boundary depends not only on the nature of the stationary phase, but also on the composition of the mobile phase. In spite of its importance, phase ratio is seldom reported for commercially available HPLC columns and the data typically provided by the vendors about the columns do not provide key information that would allow the calculation of Φ based on Vst and V0 values. A different procedure for the evaluation of Φ is based on the following formula: log k'j=a log Kow,j+log Φ, where k'j is the retention factor for a compound j that must be a hydrocarbon, Kow,j is the octanol/water partition coefficient, and a is a proportionality constant. Present study describes the experimental evaluation of Φ based on the measurement of k'j for the compounds in the homologous series between benzene and butylbenzene for three C18 columns: Gemini C18, Luna C18 both with 5 μm particles, and a Chromolith Performance RP-18. The evaluation was performed for two mobile phase systems at different proportions of methanol/water and acetonitrile/water. The octanol/water partition coefficients were obtained from the literature. The results obtained in the study provide further support for the new procedure for the evaluation of phase ratio. Copyright © 2016 Elsevier B.V. All rights reserved.

Impacts of Fire Ecology Range Management (FERM) on the Fate and Transport of Energetic Materials on Testing and Training Ranges

DTIC Science & Technology

2006-04-01

be significantly reduced or eliminated. Phytoremediation . Plants can have important effects on the fate and distribution of energetic compounds...place, and they can act as a surface for adherence of energetic compounds. Phytoremediation is frequently applied as a plant based remedial...intermediate log Kow (0.5 to 4) tend to be good targets 2 for phytoremediation because they are taken up by the roots and considered xylem mobile and

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.

Identification of genotoxic compounds in crude oil using fractionation according to distillation, polarity and Kow.

PubMed

Park, Shin Yeong; Lee, Hyo Jin; Khim, Jong Seong; Kim, Gi Beum

2017-01-30

We examined the degree of DNA damage caused by fractions of crude oil in accordance with the boiling points, polarity and log K ow . Relatively high DNA damage was observed in the aromatic fraction (290-330°C) and resin and polar fraction (350-400°C). The resin and polar fraction showed relatively high genotoxicity compared with the aliphatic and aromatic fraction at the 1-4 log K ow range. At the 6-7 log K ow range, the aromatic fraction showed relatively high DNA damage compared with the aliphatic and resin and polar fraction. In particular, every detailed fraction in accordance with the log K ow values (aliphatic and aromatic (310-320°C) and resins and polar fractions (370-380°C)) showed one or less than one DNA damage. However, the fractions before separation in accordance with log K ow values (aliphatic and aromatic (310-320°C) and resin and polar (370-380°C) fractions) showed high DNA damage. Thus, we confirm the synergistic action between the detailed compounds. Copyright © 2016 Elsevier Ltd. All rights reserved.

Confocal Raman Microscopy for in Situ Measurement of Octanol-Water Partitioning within the Pores of Individual C18-Functionalized Chromatographic Particles.

PubMed

Kitt, Jay P; Harris, Joel M

2015-05-19

Octanol-water partitioning is one of the most widely used predictors of hydrophobicity and lipophilicity. Traditional methods for measuring octanol-water partition coefficients (K(ow)), including shake-flasks and generator columns, require hours for equilibration and milliliter quantities of sample solution. These challenges have led to development of smaller-scale methods for measuring K(ow). Recent advances in microfluidics have produced faster and smaller-volume approaches to measuring K(ow). As flowing volumes are reduced, however, separation of water and octanol prior to measurement and detection in small volumes of octanol phase are especially challenging. In this work, we reduce the receiver volume of octanol-water partitioning measurements from current practice by six-orders-of-magnitude, to the femtoliter scale, by using a single octanol-filled reversed-phase, octadecylsilane-modified (C18-silica) chromatographic particle as a collector. The fluid-handling challenges of working in such small volumes are circumvented by eliminating postequilibration phase separation. Partitioning is measured in situ within the pore-confined octanol phase using confocal Raman microscopy, which is capable of detecting and quantifying a wide variety of molecular structures. Equilibration times are fast (less than a minute) because molecular diffusion is efficient over distance scales of micrometers. The demonstrated amount of analyte needed to carry out a measurement is very small, less than 50 fmol, which would be a useful attribute for drug screening applications or testing of small quantities of environmentally sensitive compounds. The method is tested for measurements of pH-dependent octanol-water partitioning of naphthoic acid, and the results are compared to both traditional shake-flask measurements and sorption onto C18-modified silica without octanol present within the pores.

Correlation of the Capacity Factor in Vesicular Electrokinetic Chromatography with the Octanol:Water Partition Coefficient for Charged and Neutral Analytes

PubMed Central

Razak, J. L.; Cutak, B. J.; Larive, C. K.; Lunte, C. E.

2008-01-01

Purpose The aim of this study was to develop a method based upon electrokinetic chromatography (EKC) using oppositely charged surfactant vesicles as a buffer modifier to estimate hydrophobicity (log P) for a range of neutral and charged compounds. Methods Vesicles were formed from cetyltrimethylammonium bromide (CTAB) and sodium n-octyl sulfate (SOS). The size and polydispersity of the vesicles were characterized by electron microscopy, dynamic light scattering, and pulsed-field gradient NMR (PFG-NMR). PFG-NMR was also used to determine if ion-pairing between cationic analytes and free SOS monomer occurred. The CTAB/SOS vesicles were used as a buffer modifier in capillary electrophoresis (CE). The capacity factor (log k′) was calculated by determining the mobility of the analytes both in the presence and absence of vesicles. Log k′ was determined for 29 neutral and charged analytes. Results There was a linear relationship between the log of capacity factor (log k′) and octanol/water partition coefficient (log P) for both neutral and basic species at pH 6.0, 7.3, and 10.2. This indicated that interaction between the cation and vesicle was dominated by hydrophobic forces. At pH 4.3, the log k′ values for the least hydrophobic basic analytes were higher than expected, indicating that electrostatic attraction as well as hydrophobic forces contributed to the overall interaction between the cation and vesicle. Anionic compounds could not be evaluated using this system. Conclusion Vesicular electrokinetic chromatography (VEKC) using surfactant vesicles as buffer modifiers is a promising method for the estimation of hydrophobicity. PMID:11336344

Plant selective uptake of halogenated flame retardants at an e-waste recycling site in southern China.

PubMed

Wang, Shaorui; Wang, Yan; Luo, Chunling; Li, Jun; Yin, Hua; Zhang, Gan

2016-07-01

The concentrations and homolog patterns of halogenated flame retardants (HFRs) in vegetables grown at an e-waste contaminated site were investigated. Polybrominated diphenyl ethers (PBDEs) were the dominant HFRs in vegetable tissues, with concentrations ranging from 10.3 to 164 ng g(-1) and 1.16-107 ng g(-1) in shoots and roots, respectively, followed by novel brominated flame retardants (NBFRs) and dechlorane plus (DPs). This is an indication that PBDE contamination in vegetables grown around e-waste recycling sites may pose a risk to the local terrestrial ecosystem and residents. In addition, this is the first report on the concentrations and compositions of NBFRs in vegetables around e-waste recycling sites. The HFRs concentrations in vegetables varied greatly with the vegetable species, with the highest concentrations observed in Brassica oleracea var. capitata. Root concentration factors (RCF) decreased with increasing log Kow of HFRs, which indicated that the uptake of HFRs was controlled mainly by log Kow. Dissimilar HFRs profiles in shoots and roots suggested that the uptake and translocation of HFRs by plants were selective, with lower halogenated congeners prone to accumulation in vegetable tissues. Positive relationships between PBDEs and their substitutes were observed in vegetable tissues, suggesting that the replacement of PBDEs by NBFRs has not resulted in an obvious transition in plants within the study area. Copyright © 2016 Elsevier Ltd. All rights reserved.

High-Throughput Analytical Techniques for Determination of Residues of 653 Multiclass Pesticides and Chemical Pollutants in Tea--Part V: A Comparative Study of the Influence of Tea Hydration on the Efficiency of Pesticide Multiresidue Determination Using Three Sample Preparation Methods and GC/MS/MS.

PubMed

Chen, Xi; Li, Yan; Chang, Qiao-Ying; Hu, Xue-Yan; Pang, Guo-Fang; Fan, Chun-Lin

2015-01-01

This paper describes a comparative study of the influence of three sample preparation techniques (M1: hydration+oscillating extraction+partial extraction solution hexane partitioning cleanup; M2: hydration+oscillating extraction+overall extraction solution SPE cleanup; and M3: pure acetonitrile homogeneous extraction+overall extraction SPE cleanup) on the determination efficiency of 456 pesticide multiresidues in tea. First, it was discovered from the mathematical correlation equation of 329 pesticide recoveries established and log Kow values that the extraction efficiency of hydration method M1 has obvious correlation with pesticide log Kow, making the extraction efficiency of M1 take the shape of an arc trend line with a certain arc hanging down from both ends of polar pesticides and nonpolar pesticides. Second, regarding the M1 method, the interfering matter after co-extraction increased in large quantities, which markedly lowered the S/N of the target pesticides and method sensitivity, leading to an obvious decrease of the method efficiency. The fortification experiment of the uniform limit 0.010 mg/kg proved that with the M1 hydration method there are 23 pesticides with recoveries between 70 and 120% and RSD<20%, accounting for only 5.0%, while with nonhydration method M3 there are 229 pesticides, making up 50%.

Fragment-based approach to calculate hydrophobicity of anionic and nonionic surfactants derived from chromatographic retention on a C18 stationary phase.

PubMed

Hammer, Jort; Haftka, Joris J-H; Scherpenisse, Peter; Hermens, Joop L M; de Voogt, Pim W P

2017-02-01

To predict the fate and potential effects of organic contaminants, information about their hydrophobicity is required. However, common parameters to describe the hydrophobicity of organic compounds (e.g., octanol-water partition constant [K OW ]) proved to be inadequate for ionic and nonionic surfactants because of their surface-active properties. As an alternative approach to determine their hydrophobicity, the aim of the present study was therefore to measure the retention of a wide range of surfactants on a C 18 stationary phase. Capacity factors in pure water (k' 0 ) increased linearly with increasing number of carbon atoms in the surfactant structure. Fragment contribution values were determined for each structural unit with multilinear regression, and the results were consistent with the expected influence of these fragments on the hydrophobicity of surfactants. Capacity factors of reference compounds and log K OW values from the literature were used to estimate log K OW values for surfactants (log KOWHPLC). These log KOWHPLC values were also compared to log K OW values calculated with 4 computational programs: KOWWIN, Marvin calculator, SPARC, and COSMOThermX. In conclusion, capacity factors from a C 18 stationary phase are found to better reflect hydrophobicity of surfactants than their K OW values. Environ Toxicol Chem 2017;36:329-336. © 2016 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC. © 2016 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.

Log D versus HPLC derived hydrophobicity: The development of predictive tools to aid in the rational design of bioactive peptoids

DOE PAGES

Bolt, H. L.; Williams, C. E. J.; Brooks, R. V.; ...

2017-01-13

Hydrophobicity has proven to be an extremely useful parameter in small molecule drug discovery programmes given that it can be used as a predictive tool to enable rational design. For larger molecules, including peptoids, where folding is possible, the situation is more complicated and the average hydrophobicity (as determined by RP-HPLC retention time) may not always provide an effective predictive tool for rational design. Herein, we report the first ever application of partitioning experiments to determine the log D values for a series of peptoids. By comparing log D and average hydrophobicities we highlight the potential advantage of employing themore » former as a predictive tool in the rational design of biologically active peptoids.« less

Log D versus HPLC derived hydrophobicity: The development of predictive tools to aid in the rational design of bioactive peptoids

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

Bolt, H. L.; Williams, C. E. J.; Brooks, R. V.

Hydrophobicity has proven to be an extremely useful parameter in small molecule drug discovery programmes given that it can be used as a predictive tool to enable rational design. For larger molecules, including peptoids, where folding is possible, the situation is more complicated and the average hydrophobicity (as determined by RP-HPLC retention time) may not always provide an effective predictive tool for rational design. Herein, we report the first ever application of partitioning experiments to determine the log D values for a series of peptoids. By comparing log D and average hydrophobicities we highlight the potential advantage of employing themore » former as a predictive tool in the rational design of biologically active peptoids.« less

QSPR study of polychlorinated diphenyl ethers by molecular electronegativity distance vector (MEDV-4).

PubMed

Sun, Lili; Zhou, Liping; Yu, Yu; Lan, Yukun; Li, Zhiliang

2007-01-01

Polychlorinated diphenyl ethers (PCDEs) have received more and more concerns as a group of ubiquitous potential persistent organic pollutants (POPs). By using molecular electronegativity distance vector (MEDV-4), multiple linear regression (MLR) models are developed for sub-cooled liquid vapor pressures (P(L)), n-octanol/water partition coefficients (K(OW)) and sub-cooled liquid water solubilities (S(W,L)) of 209 PCDEs and diphenyl ether. The correlation coefficients (R) and the leave-one-out cross-validation (LOO) correlation coefficients (R(CV)) of all the 6-descriptor models for logP(L), logK(OW) and logS(W,L) are more than 0.98. By using stepwise multiple regression (SMR), the descriptors are selected and the resulting models are 5-descriptor model for logP(L), 4-descriptor model for logK(OW), and 6-descriptor model for logS(W,L), respectively. All these models exhibit excellent estimate capabilities for internal sample set and good predictive capabilities for external samples set. The consistency between observed and estimated/predicted values for logP(L) is the best (R=0.996, R(CV)=0.996), followed by logK(OW) (R=0.992, R(CV)=0.992) and logS(W,L) (R=0.983, R(CV)=0.980). By using MEDV-4 descriptors, the QSPR models can be used for prediction and the model predictions can hence extend the current database of experimental values.

Application of perfluorinated acids as ion-pairing reagents for reversed-phase chromatography and retention-hydrophobicity relationships studies of selected beta-blockers.

PubMed

Flieger, J

2010-01-22

The addition of the homologous series of perfluorinated acids-trifluoroacetic acid (TFAA), pentafluoropropionic acid (PFPA), heptafluorobutyric acid (HFBA) to mobile phases for reversed-phase high-performance liquid chromatography (RP-HPLC) of beta-blockers was tested. Acidic modifiers were responsible for acidification of mobile phase (pH 3) ensuring the protonation of the beta-blockers and further ion pairs creation. The effect of the type and concentration of mobile phase additives on retention parameters, the efficiency of the peaks, their symmetry and separation selectivity of the beta-blockers mixture were all studied. It appeared that at increasing acid concentration, the retention factor, for all compounds investigated, increased to varying degrees. It should be stressed that the presence of acids more significantly affected the retention of the most hydrophobic beta-blockers. Differences in hydrophobicity of drugs can be maximized through variation of the hydrophobicity of additives. Thus, the relative increase in the retention depends on either concentration and hydrophobicity of the anionic mobile phase additive or hydrophobicity of analytes. According to QSRR (quantitative structure retention relationship) methodology, chromatographic lipophilicity parameters: isocratic log k and log k(w) values (extrapolated retention to pure water) were correlated with the molecular (log P(o/w)) and apparent (log P(app)) octanol-water partition coefficients obtained experimentally by countercurrent chromatography (CCC) or predicted by Pallas software. The obtained, satisfactory retention-hydrophobicity correlations indicate that, in the case of the basic drugs examined in RP-HPLC systems modified with perfluorinated acids, the retention is mainly governed by their hydrophobicity. Copyright 2009 Elsevier B.V. All rights reserved.

Partitioning of polar and non-polar neutral organic chemicals into human and cow milk.

PubMed

Geisler, Anett; Endo, Satoshi; Goss, Kai-Uwe

2011-10-01

The aim of this work was to develop a predictive model for milk/water partition coefficients of neutral organic compounds. Batch experiments were performed for 119 diverse organic chemicals in human milk and raw and processed cow milk at 37°C. No differences (<0.3 log units) in the partition coefficients of these types of milk were observed. The polyparameter linear free energy relationship model fit the calibration data well (SD=0.22 log units). An experimental validation data set including hormones and hormone active compounds was predicted satisfactorily by the model. An alternative modelling approach based on log K(ow) revealed a poorer performance. The model presented here provides a significant improvement in predicting enrichment of potentially hazardous chemicals in milk. In combination with physiologically based pharmacokinetic modelling this improvement in the estimation of milk/water partitioning coefficients may allow a better risk assessment for a wide range of neutral organic chemicals. Copyright © 2011 Elsevier Ltd. All rights reserved.

Comparison of the applicability domain of a quantitative structure-activity relationship for estrogenicity with a large chemical inventory.

PubMed

Netzeva, Tatiana I; Gallegos Saliner, Ana; Worth, Andrew P

2006-05-01

The aim of the present study was to illustrate that it is possible and relatively straightforward to compare the domain of applicability of a quantitative structure-activity relationship (QSAR) model in terms of its physicochemical descriptors with a large inventory of chemicals. A training set of 105 chemicals with data for relative estrogenic gene activation, obtained in a recombinant yeast assay, was used to develop the QSAR. A binary classification model for predicting active versus inactive chemicals was developed using classification tree analysis and two descriptors with a clear physicochemical meaning (octanol-water partition coefficient, or log Kow, and the number of hydrogen bond donors, or n(Hdon)). The model demonstrated a high overall accuracy (90.5%), with a sensitivity of 95.9% and a specificity of 78.1%. The robustness of the model was evaluated using the leave-many-out cross-validation technique, whereas the predictivity was assessed using an artificial external test set composed of 12 compounds. The domain of the QSAR training set was compared with the chemical space covered by the European Inventory of Existing Commercial Chemical Substances (EINECS), as incorporated in the CDB-EC software, in the log Kow / n(Hdon) plane. The results showed that the training set and, therefore, the applicability domain of the QSAR model covers a small part of the physicochemical domain of the inventory, even though a simple method for defining the applicability domain (ranges in the descriptor space) was used. However, a large number of compounds are located within the narrow descriptor window.

Overview and comparison of lipid-containing semipermeable membrane devices and oysters (Crassostrea gigas) for assessing organic chemical exposure

USGS Publications Warehouse

Huckins, J.N.; Prest, H.F.; Petty, J.D.; Lebo, J.A.; Hodgins, M.M.; Clark, R.C.; Alvarez, D.A.; Gala, W.R.; Steen, A.; Gale, R.; Ingersoll, C.G.

2004-01-01

We performed 20-d, flow-through exposures of lipid-containing semipermeable membrane devices (SPMDs) and Pacific oysters (Crassostrea gigas) to three concentrations (nominally 10, 100, and 250 ng/L) of a diverse mixture of polycyclic aromatic hydrocarbons (PAHs). Exposure water was seawater free of particulates larger than 0.1 μm. The results of these controlled laboratory studies demonstrated that SPMDs and oysters concentrate the same chemicals but that the relative amounts accumulated are different. For oysters, the 20-d mean (across treatments) concentration factors (CFs) of test compounds with log Kow ≤ 4.8 were much lower (4.0- to 20-fold lower) than those of the same compounds in SPMDs. In contrast, the 20-d CFs of PAHs with log Kow ≥ 5.6 in oysters from the low-level treatment were higher than the corresponding CFs for SPMDs. The CFs of these compounds in oysters from the low-level treatment ranged from approximately 3.0- to 13-fold higher than those in oysters from the high-level treatment. This physiologically mediated difference in oyster CFs appears to be linked to active feeding in the low-level treatment and to apparent toxicity-induced cessation of feeding (i.e., valve closure) in the high-level treatment. Because CFs for these compounds in oysters were not independent of exposure concentrations, it follows that tissue levels were not proportional to exposure concentration. However, both sampling approaches have advantages and disadvantages, and the appropriateness of their use depends on the goals of a given study.

Effect of O-acylmenthol on transdermal delivery of drugs with different lipophilicity.

PubMed

Zhao, Ligang; Fang, Liang; Xu, Yongnan; Zhao, Yanyan; He, Zhonggui

2008-03-20

To develop more effective compounds as enhancers, O-acylmenthol derivatives which were expected to be enzymatically hydrolyzed into nontoxic metabolites by esterases in the living epidermis were synthesized from l-menthol and pharmaceutical excipient acids (lactic acid, cinnamic acid, salicylic acid and oleic acid) in this study. Their promoting activity on the percutaneous absorption of five model drugs, 5-fluorouracil (5-FU), isosorbide dinitrate (ISDN), lidocaine (LD), ketoprofen (KP), and indomethacin (IM), which were selected based on their lipophilicity represented by log K(O/W), were tested in vitro across full thickness rat skin with each of the evaluated drugs in saturated donor solution. 2-Isopropyl-5-methylcyclohexyl 2-hydroxypanoate (M-LA) provided the highest increase of accumulation of 5-FU (3.74-fold) and LD (4.19-fold) in the receptor phase while 2-isopropyl-5-methylcyclohexyl cinnamate (M-CA) was ineffective for most of the drugs; Both 2-isopropyl-5-methylcyclohexyl 2-hydroxybenzoate (M-SA) and (E)-2-isopropyl-5-methylcyclohexyl octadec-9-enoate (M-OA) had better promoting effects on the drugs with low water-solubility. The four O-acylmenthol enhancers produced parabolic relationship between the lipophilicity (log K(O/W)) of the model drugs (5-FU, ISDN, KP, IM) and their enhancement ratio of the permeation coefficient (ER(P)), indicating that the lipophilicity of the penetrants has significant effect on the permeation results, r = 0.989 (P=0.144) for M-LA, r = 0.965 (P = 0.216) for M-CA, r = 0.786 (P = 0.630) for M-SA, and r = 0.996 (P = 0.088) for M-OA.

Capability of microalgae-based wastewater treatment systems to remove emerging organic contaminants: a pilot-scale study.

PubMed

Matamoros, Víctor; Gutiérrez, Raquel; Ferrer, Ivet; García, Joan; Bayona, Josep M

2015-05-15

The effect of hydraulic retention time (HRT) and seasonality on the removal efficiency of 26 organic microcontaminants from urban wastewater was studied in two pilot high-rate algal ponds (HRAPs). The targeted compounds included pharmaceuticals and personal care products, fire retardants, surfactants, anticorrosive agents, pesticides and plasticizers, among others. The pilot plant, which was fed at a surface loading rate of 7-29 g of COD m(-2)d(-1), consisted of a homogenisation tank and two parallel lines, each one with a primary settler and an HRAP with a surface area of 1.5 m(2) and a volume of 0.5 m(3). The two HRAPs were operated with different HRTs (4 and 8 d). The removal efficiency ranged from negligible removal to more than 90% depending on the compound. Microcontaminant removal efficiencies were enhanced during the warm season, while the HRT effect on microcontaminant removal was only noticeable in the cold season. Our results suggest that biodegradation and photodegradation are the most important removal pathways, whereas volatilization and sorption were solely achieved for hydrophobic compounds (log Kow>4) with a moderately high Henry's law constant values (11-12 Pa m(-3)mol(-1)) such as musk fragrances. Whereas acetaminophen, ibuprofen and oxybenzone presented ecotoxicological hazard quotients (HQs) higher than 1 in the influent wastewater samples, the HQs for the effluent water samples were always below 1. Copyright © 2015 Elsevier B.V. All rights reserved.

Occurrence, distribution and bioaccumulation behaviour of hydrophobic organic contaminants in a large-scale constructed wetland in Singapore.

PubMed

Wang, Qian; Kelly, Barry C

2017-09-01

This study involved a field-based investigation to assess the occurrence, distribution and bioaccumulation behaviour of hydrophobic organic contaminants in a large-scale constructed wetland. Samples of raw leachate, water and wetland plants, Typha angustifolia, were collected for chemical analysis. Target contaminants included polychlorinated biphenyls (PCBs), organochlorine pesticides (OCP), as well as several halogenated flame retardants (HFRs) and personal care products (triclosan and synthetic musks). In addition to PCBs and OCPs, synthetic musks, triclosan (TCS) and dechlorane plus stereoisomers (syn- and anti-DPs) were frequently detected. Root concentration factors (log RCF L/kg wet weight) of the various contaminants ranged between 3.0 and 7.9. Leaf concentration factors (log LCF L/kg wet weight) ranged between 2.4 and 8.2. syn- and anti-DPs exhibited the greatest RCF and LCF values. A strong linear relationship was observed between log RCF and octanol-water partition coefficient (log K OW ). Translocation factors (log TFs) were negatively correlated with log K OW . The results demonstrate that more hydrophobic compounds exhibit higher degrees of partitioning into plant roots and are less effectively transported from roots to plant leaves. Methyl triclosan (MTCS) and 2,8-dichlorodibenzo-p-dioxin (DCDD), TCS degradation products, exhibited relatively high concentrations in roots and leaves., highlighting the importance of degradation/biotransformation. The results further suggest that Typha angustifolia in this constructed wetland can aid the removal of hydrophobic organic contaminants present in this landfill leachate. The findings will aid future investigations regarding the fate and bioaccumulation of hydrophobic organic contaminants in constructed wetlands. Copyright © 2017 Elsevier Ltd. All rights reserved.

Influence of variation in mobile phase pH and solute pK(a) with the change of organic modifier fraction on QSRRs of hydrophobicity and RP-HPLC retention of weakly acidic compounds.

PubMed

Han, Shu-ying; Liang, Chao; Zou, Kuan; Qiao, Jun-qin; Lian, Hong-zhen; Ge, Xin

2012-11-15

The variation in mobile phase pH and ionizable solute dissociation constant (pK(a)) with the change of organic modifier fraction in hydroorganic mobile phase has seemingly been a troublesome problem in studies and applications of reversed phase high performance liquid chromatography (RP-HPLC). Most of the early studies regarding the RP-HPLC of acid-base compounds have to measure the actual pH of the mixed mobile phase rigorously, sometimes bringing difficulties in the practices of liquid chromatographic separation. In this paper, the effect of this variation on the apparent n-octanol/water partition coefficient (K(ow)″) and the related quantitative structure-retention relationship (QSRR) of logK(ow)″ vs. logk(w), the logarithm of retention factor of analytes in neat aqueous mobile phases, was investigated for weakly acidic compounds. This QSRR is commonly used as a classical method for K(ow) measurement by RP-HPLC. The theoretical and experimental derivation revealed that the variation in mobile phase pH and solute pK(a) will not affect the QSRRs of acidic compounds. This conclusion is proved to be suitable for various types of ion-suppressors, i.e., strong acid (perchloric acid), weak acid (acetic acid) and buffer salt (potassium dihydrogen phosphate/phosphoric acid, PBS). The QSRRs of logK(ow)″ vs. logk(w) were modeled by 11 substituted benzoic acids using different types of ion-suppressors in a binary methanol-water mobile phase to confirm our deduction. Although different types of ion-suppressor all can be used as mobile phase pH modifiers, the QSRR model obtained by using perchloric acid as the ion-suppressor was found to have the best result, and the slightly inferior QSRRs were obtained by using acetic acid or PBS as the ion-suppressor. Copyright © 2012 Elsevier B.V. All rights reserved.

Development of a passive, in situ, integrative sampler for hydrophilic organic contaminants in aquatic environments

USGS Publications Warehouse

Alvarez, D.A.; Petty, J.D.; Huckins, J.N.; Jones-Lepp, T. L.; Getting, D.T.; Goddard, J.P.; Manahan, S.E.

2004-01-01

Increasingly it is being realized that a holistic hazard assessment of complex environmental contaminant mixtures requires data on the concentrations of hydrophilic organic contaminants including new generation pesticides, pharmaceuticals, personal care products, and many chemicals associated with household, industrial, and agricultural wastes. To address this issue, we developed a passive in situ sampling device (the polar organic chemical integrative sampler [POCIS]) that integratively concentrates trace levels of complex mixtures of hydrophilic environmental contaminants, enables the determination of their time-weighted average water concentrations, and provides a method of estimating the potential exposure of aquatic organisms to the complex mixture of waterborne contaminants. Using a prototype sampler, linear uptake of selected herbicides and pharmaceuticals with log KowS < 4.0 was observed for up to 56 d. Estimation of the ambient water concentrations of chemicals of interest is achieved by using appropriate uptake models and determination of POCIS sampling rates for appropriate exposure conditions. Use of POCIS in field validation studies targeting the herbicide diuron in the United Kingdom resulted in the detection of the chemical at estimated concentrations of 190 to 600 ng/L. These values are in agreement with reported levels found in traditional grab samples taken concurrently.

DETERMINATION OF KOW VALUES FOR A SERIES OF ARYL GLUCURONIDES

EPA Science Inventory

An important perameter in toxicokinetic modeling is the octanol/water partition coefficient (Kow). This parameter has often been used to predict the accumulation of contaminants from water to fish (Klamer and Beekman 1995); however, few Kow values are available for modeling the b...

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.

Passive Sampling of Nonpolar Compounds in Sediments

DTIC Science & Technology

2010-12-02

Example 1: pore water sniffing PAHs/PCBs/HCB in harbor sediments ES&T 37: 4213-4220,2003 LDPE strips in sediment slurries and stagnant sediments...slurry stagnant ~160 g sediment (1-4% oc) ~120 mL water 0.5 g LDPE (30x2.5 cm) 50 d exposure chrysene msed Kd ≈1000 L ms Ksw ≈ 300 L ( or ) Koc from...silicone ! SPME! POG! LDPE ! Chemcatcher ! SPMD! POCIS! Mesco I 300 200 100 2 3 4 5 6 7 8 N ( n g ) log Kow Cw = 1 ng / L week 123456 Evolution of peak pattern

Role of submerged vegetation in the retention processes of three plant protection products in flow-through stream mesocosms.

PubMed

Stang, Christoph; Wieczorek, Matthias Valentin; Noss, Christian; Lorke, Andreas; Scherr, Frank; Goerlitz, Gerhard; Schulz, Ralf

2014-07-01

Quantitative information on the processes leading to the retention of plant protection products (PPPs) in surface waters is not available, particularly for flow-through systems. The influence of aquatic vegetation on the hydraulic- and sorption-mediated mitigation processes of three PPPs (triflumuron, pencycuron, and penflufen; logKOW 3.3-4.9) in 45-m slow-flowing stream mesocosms was investigated. Peak reductions were 35-38% in an unvegetated stream mesocosm, 60-62% in a sparsely vegetated stream mesocosm (13% coverage with Elodea nuttallii), and in a similar range of 57-69% in a densely vegetated stream mesocosm (100% coverage). Between 89% and 93% of the measured total peak reductions in the sparsely vegetated stream can be explained by an increase of vegetation-induced dispersion (estimated with the one-dimensional solute transport model OTIS), while 7-11% of the peak reduction can be attributed to sorption processes. However, dispersion contributed only 59-71% of the peak reductions in the densely vegetated stream mesocosm, where 29% to 41% of the total peak reductions can be attributed to sorption processes. In the densely vegetated stream, 8-27% of the applied PPPs, depending on the logKOW values of the compounds, were temporarily retained by macrophytes. Increasing PPP recoveries in the aqueous phase were accompanied by a decrease of PPP concentrations in macrophytes indicating kinetic desorption over time. This is the first study to provide quantitative data on how the interaction of dispersion and sorption, driven by aquatic macrophytes, influences the mitigation of PPP concentrations in flowing vegetated stream systems. Copyright © 2014 Elsevier Ltd. All rights reserved.

PAH bioconcentration in Mytilus sp from Sinclair Inlet, WA

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

Frazier, J.; Young, D.; Ozretich, R.

1995-12-31

Approximately 20 polynuclear aromatic hydrocarbons (PAH) were measured by GC/MS in seawater and whole soft tissues of the intertidal mussel Mytilus sp. collected in July 1991 within and around Puget Sound`s Sinclair Inlet. Low variability was observed in the water concentrations collected over three days at control sites, yielding reliable values for the exposure levels experienced by this bioindicator mollusk. Mean water concentrations of acenaphthene, phenanthrene, and fluoranthene in the control region were 2.7 {+-} 0.8, 2.8 {+-} 0.8, and 3.1 {+-} 0.7 ng/liter, respectively. Levels measured near sites of vessel activity were higher but much more variable; this reducedmore » the reliability of the tissue/water bioconcentration factors (BCF) obtained from these samples. An empirical model relating values of Log BCF and Log Kow for the control zone samples supports the utility of this estuarine bioindicator for monitoring general levels of PAH in nearshore surface waters.« less

Description, Properties, and Degradation of Selected Volatile Organic Compounds Detected in Ground Water--A Review of Selected Literature

USGS Publications Warehouse

Lawrence, Stephen J.

2006-01-01

This report provides abridged information describing the most salient properties and biodegradation of 27 chlorinated volatile organic compounds detected during ground-water studies in the United States. This information is condensed from an extensive list of reports, papers, and literature published by the U.S. Government, various State governments, and peer-reviewed journals. The list includes literature reviews, compilations, and summaries describing volatile organic compounds in ground water. This report cross-references common names and synonyms associated with volatile organic compounds with the naming conventions supported by the International Union of Pure and Applied Chemistry. In addition, the report describes basic physical characteristics of those compounds such as Henry's Law constant, water solubility, density, octanol-water partition (log Kow), and organic carbon partition (log Koc) coefficients. Descriptions and illustrations are provided for natural and laboratory biodegradation rates, chemical by-products, and degradation pathways.

Micellar versus hydro-organic mobile phases for retention-hydrophobicity relationship studies with ionizable diuretics and an anionic surfactant.

PubMed

Ruiz-Angel, M J; Carda-Broch, S; García-Alvarez-Coque, M C; Berthod, A

2004-03-19

Logarithm of retention factors (log k) of a group of 14 ionizable diuretics were correlated with the molecular (log P o/w) and apparent (log P(app)) octanol-water partition coefficients. The compounds were chromatographed using aqueous-organic (reversed-phase liquid chromatography, RPLC) and micellar-organic mobile phases (micellar liquid chromatography, MLC) with the anionic surfactant sodium dodecyl sulfate (SDS), in the pH range 3-7, and a conventional octadecylsilane column. Acetonitrile was used as the organic modifier in both modes. The quality of the correlations obtained for log P(app) at varying ionization degree confirms that this correction is required in the aqueous-organic mixtures. The correlation is less improved with SDS micellar media because the acid-base equilibriums are shifted towards higher pH values for acidic compounds. In micellar chromatography, an electrostatic interaction with charged solutes is added to hydrophobic forces; consequently, different correlations should be established for neutral and acidic compounds, and for basic compounds. Correlations between log k and the isocratic descriptors log k(w), log k(wm) (extrapolated retention to pure water in the aqueous-organic and micellar-organic systems, respectively), and psi0 (extrapolated mobile phase composition giving a k = 1 retention factor or twice the dead time), and between these descriptors and log P(app) were also satisfactory, although poorer than those between log k and log P(app) due to the extrapolation. The study shows that, in the particular case of the ionizable diuretics studied, classical RPLC gives better results than MLC with SDS in the retention hydrophobicity correlations.

Monitoring alkylphenols in water using the polar organic chemical integrative sampler (POCIS): Determining sampling rates via the extraction of PES membranes and Oasis beads.

PubMed

Silvani, Ludovica; Riccardi, Carmela; Eek, Espen; Papini, Marco Petrangeli; Morin, Nicolas A O; Cornelissen, Gerard; Oen, Amy M P; Hale, Sarah E

2017-10-01

Polar organic chemical integrative samplers (POCIS) have previously been used to monitor alkylphenol (AP) contamination in water and produced water. However, only the sorbent receiving phase of the POCIS (Oasis beads) is traditionally analyzed, thus limiting the use of POCIS for monitoring a range of APs with varying hydrophobicity. Here a "pharmaceutical" POCIS was calibrated in the laboratory using a static renewal setup for APs (from 2-ethylphenol to 4-n-nonylphenol) with varying hydrophobicity (log K ow between 2.47 and 5.76). The POCIS sampler was calibrated over its 28 day integrative regime and sampling rates (R s ) were determined. Uptake was shown to be a function of AP hydrophobicity where compounds with log K ow  < 4 were preferentially accumulated in Oasis beads, and compounds with log K ow  > 5 were preferentially accumulated in the PES membranes. A lag phase (over a 24 h period) before uptake in to the PES membranes occurred was evident. This work demonstrates that the analysis of both POCIS phases is vital in order to correctly determine environmentally relevant concentrations owing to the fact that for APs with log K ow  ≤ 4 uptake, to the PES membranes and the Oasis beads, involves different processes compared to APs with log K ow  ≥ 4. The extraction of both the POCIS matrices is thus recommended in order to assess the concentration of hydrophobic APs (log K ow  ≥ 4), as well as hydrophilic APs, most effectively. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Acute and chronic environmental effects of clandestine methamphetamine waste.

PubMed

Kates, Lisa N; Knapp, Charles W; Keenan, Helen E

2014-09-15

The illicit manufacture of methamphetamine (MAP) produces substantial amounts of hazardous waste that is dumped illegally. This study presents the first environmental evaluation of waste produced from illicit MAP manufacture. Chemical oxygen demand (COD) was measured to assess immediate oxygen depletion effects. A mixture of five waste components (10mg/L/chemical) was found to have a COD (130 mg/L) higher than the European Union wastewater discharge regulations (125 mg/L). Two environmental partition coefficients, K(OW) and K(OC), were measured for several chemicals identified in MAP waste. Experimental values were input into a computer fugacity model (EPI Suite™) to estimate environmental fate. Experimental log K(OW) values ranged from -0.98 to 4.91, which were in accordance with computer estimated values. Experimental K(OC) values ranged from 11 to 72, which were much lower than the default computer values. The experimental fugacity model for discharge to water estimates that waste components will remain in the water compartment for 15 to 37 days. Using a combination of laboratory experimentation and computer modelling, the environmental fate of MAP waste products was estimated. While fugacity models using experimental and computational values were very similar, default computer models should not take the place of laboratory experimentation. Copyright © 2014 Elsevier B.V. All rights reserved.

Human in Vivo pharmacokinetics of [ 14C]Dibenzo[ def,p]chrysene by accelerator mass spectrometry following oral microdosing

DOE PAGES

Madeen, Erin; Corley, Richard A.; Crowell, Susan; ...

2014-11-24

Dibenzo( def,p)chrysene (DBC), (also known as dibenzo[a,l]pyrene), is a high molecular weight polycyclic aromatic hydrocarbon (PAH) found in the environment, including food, produced by the incomplete combustion of hydrocarbons. DBC, classified by IARC as a 2A probable human carcinogen, has a relative potency factor (RPF) in animal cancer models 30-fold higher than benzo[ a]pyrene. No data are available describing the disposition of high molecular weight (>4 rings) PAHs in humans to compare to animal studies. Pharmacokinetics of DBC was determined in 3 female and 6 male human volunteers following oral microdosing (29 ng, 5 nCi) of [ 14C]-DBC. This studymore » was made possible with highly sensitive accelerator mass spectrometry (AMS), capable of detecting [ 14C]-DBC equivalents in plasma and urine following a dose considered of de minimus risk to human health. Plasma and urine were collected over 72 h. The plasma C max was 68.8 ± 44.3 fg·mL –1 with a T max of 2.25 ± 1.04 h. Elimination occurred in two distinct phases: a rapid (α)-phase, with a T 1/2 of 5.8 ± 3.4 h and an apparent elimination rate constant (K el) of 0.17 ± 0.12 fg·h –1, followed by a slower (β)-phase, with a T 1/2 of 41.3 ± 29.8 h and an apparent K el of 0.03 ± 0.02 fg·h –1. In spite of the high degree of hydrophobicity (log Kow of 7.4), DBC was eliminated rapidly in humans, as are most PAHs in animals, compared to other hydrophobic persistent organic pollutants such as, DDT, PCBs and TCDD. Preliminary examination utilizing a new UHPLC-AMS interface, suggests the presence of polar metabolites in plasma as early as 45 min following dosing. Finally, this is the first in vivo data set describing pharmacokinetics in humans of a high molecular weight PAH and should be a valuable addition to risk assessment paradigms.« less

Human in Vivo pharmacokinetics of [ 14C]Dibenzo[ def,p]chrysene by accelerator mass spectrometry following oral microdosing

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

Madeen, Erin; Corley, Richard A.; Crowell, Susan

Dibenzo( def,p)chrysene (DBC), (also known as dibenzo[a,l]pyrene), is a high molecular weight polycyclic aromatic hydrocarbon (PAH) found in the environment, including food, produced by the incomplete combustion of hydrocarbons. DBC, classified by IARC as a 2A probable human carcinogen, has a relative potency factor (RPF) in animal cancer models 30-fold higher than benzo[ a]pyrene. No data are available describing the disposition of high molecular weight (>4 rings) PAHs in humans to compare to animal studies. Pharmacokinetics of DBC was determined in 3 female and 6 male human volunteers following oral microdosing (29 ng, 5 nCi) of [ 14C]-DBC. This studymore » was made possible with highly sensitive accelerator mass spectrometry (AMS), capable of detecting [ 14C]-DBC equivalents in plasma and urine following a dose considered of de minimus risk to human health. Plasma and urine were collected over 72 h. The plasma C max was 68.8 ± 44.3 fg·mL –1 with a T max of 2.25 ± 1.04 h. Elimination occurred in two distinct phases: a rapid (α)-phase, with a T 1/2 of 5.8 ± 3.4 h and an apparent elimination rate constant (K el) of 0.17 ± 0.12 fg·h –1, followed by a slower (β)-phase, with a T 1/2 of 41.3 ± 29.8 h and an apparent K el of 0.03 ± 0.02 fg·h –1. In spite of the high degree of hydrophobicity (log Kow of 7.4), DBC was eliminated rapidly in humans, as are most PAHs in animals, compared to other hydrophobic persistent organic pollutants such as, DDT, PCBs and TCDD. Preliminary examination utilizing a new UHPLC-AMS interface, suggests the presence of polar metabolites in plasma as early as 45 min following dosing. Finally, this is the first in vivo data set describing pharmacokinetics in humans of a high molecular weight PAH and should be a valuable addition to risk assessment paradigms.« less

Brief communication: Artificial cranial modification in Kow Swamp and Cohuna.

PubMed

Durband, Arthur C

2014-09-01

The crania from Kow Swamp and Cohuna have been important for a number of debates in Australian paleoanthropology. These crania typically have long, flat foreheads that many workers have cited as evidence of genetic continuity with archaic Indonesian populations, particularly the Ngandong sample. Other scientists have alleged that at least some of the crania from Kow Swamp and the Cohuna skull have been altered through artificial modification, and that the flat foreheads possessed by these individuals are not phylogenetically informative. In this study, several Kow Swamp crania and Cohuna are compared to known modified and unmodified comparative samples. Canonical variates analyses and Mahalanobis distances are generated, and random expectation statistics are used to calculate statistical significance for these tests. The results of this study agree with prior work indicating that a portion of this sample shows evidence for artificial modification of the cranial vault. Many Kow Swamp crania and Cohuna display shape similarities with a population of known modified individuals from New Britain. Kow Swamp 1, 5, and Cohuna show the strongest evidence for modification, but other individuals from this sample also show evidence of culturally manipulated changes in cranial shape. This project provides added support for the argument that at least some Pleistocene Australian groups were practicing artificial cranial modification, and suggests that caution should be used when including these individuals in phylogenetic studies. Copyright © 2014 Wiley Periodicals, Inc.

Is halogen content the most important factor in the removal of halogenated trace organics by MBR treatment?

PubMed

Hai, Faisal I; Tadkaew, Nichanan; McDonald, James A; Khan, Stuart J; Nghiem, Long D

2011-05-01

This study investigated the relationship between physicochemical properties (namely halogen content and hydrophobicity) of halogenated trace organics and their removal efficiencies by a laboratory scale membrane bioreactor (MBR) under stable operating conditions. The reported results demonstrated a combined effect of halogen content and hydrophobicity on the removal. Compounds with high halogen content (>0.3) were well removed (>85%) when they possessed high hydrophobicity (Log D>3.2), while those with lower Log D values were also well removed if they had low halogen content (<0.1). General indices such as the BIOWIN index (which is based on only biodegradation) or a more specific index such as the halogen content (which captures a chemical aspect) appeared insufficient to predict the removal efficiency of halogenated compounds in MBR. Experimental data confirmed that the ratio of halogen content and Log D, which incorporates two important physico-chemical properties, is comparatively more suitable. Copyright © 2011 Elsevier Ltd. All rights reserved.

Prediction of Log "P": ALOGPS Application in Medicinal Chemistry Education

ERIC Educational Resources Information Center

Kujawski, Jacek; Bernard, Marek K.; Janusz, Anna; Kuzma, Weronika

2012-01-01

Molecular hydrophobicity (lipophilicity), usually quantified as log "P" where "P" is the partition coefficient, is an important molecular characteristic in medicinal chemistry and drug design. The log "P" coefficient is one of the principal parameters for the estimation of lipophilicity of chemical compounds and pharmacokinetic properties. The…

Parameterization of an empirical model for the prediction of n-octanol, alkane and cyclohexane/water as well as brain/blood partition coefficients.

PubMed

Zerara, Mohamed; Brickmann, Jürgen; Kretschmer, Robert; Exner, Thomas E

2009-02-01

Quantitative information of solvation and transfer free energies is often needed for the understanding of many physicochemical processes, e.g the molecular recognition phenomena, the transport and diffusion processes through biological membranes and the tertiary structure of proteins. Recently, a concept for the localization and quantification of hydrophobicity has been introduced (Jäger et al. J Chem Inf Comput Sci 43:237-247, 2003). This model is based on the assumptions that the overall hydrophobicity can be obtained as a superposition of fragment contributions. To date, all predictive models for the logP have been parameterized for n-octanol/water (logP(oct)) solvent while very few models with poor predictive abilities are available for other solvents. In this work, we propose a parameterization of an empirical model for n-octanol/water, alkane/water (logP(alk)) and cyclohexane/water (logP(cyc)) systems. Comparison of both logP(alk) and logP(cyc) with the logarithms of brain/blood ratios (logBB) for a set of structurally diverse compounds revealed a high correlation showing their superiority over the logP(oct) measure in this context.

COSOLVENCY AND SOPRTION OF HYDROPHOBIC ORGANIC CHEMICALS

EPA Science Inventory

Sorption of hydrophobic organic chemicals (HOCs) by two soils was measured from mixed solvents containing water plus completely miscible organic solvents (CMOSs) and partially miscible organic solvents (PMOSs). The utility of the log-linear cosolvency model for predicting HOC sor...

Effect of pore structure on the removal of clofibric acid by magnetic anion exchange resin.

PubMed

Tan, Liang; Shuang, Chendong; Wang, Yunshu; Wang, Jun; Su, Yihong; Li, Aimin

2018-01-01

The effect of pore structure of resin on clofibric acid (CA) adsorption behavior was investigated by using magnetic anion exchange resins (ND-1, ND-2, ND-3) with increasing pore diameter by 11.68, 15.37, 24.94 nm. Resin with larger pores showed faster adsorption rates and a higher adsorption capacity because the more opened tunnels provided by larger pores benefit the CA diffusion into the resin matrix. The ion exchange by the electrostatic interactions between Cl-type resin and CA resulted in chloride releasing to the solution, and the ratio of released chloride to CA adsorption amount decreased from 0.90 to 0.65 for ND-1, ND-2 and ND-3, indicating that non-electrostatic interactions obtain a larger proportional part of the adsorption into the pores. Co-existing inorganic anions and organic acids reduced the CA adsorption amounts by the competition effect of electrostatic interaction, whereas resins with more opened pore structures weakened the negative influence on CA adsorption because of the existence of non-electrostatic interactions. 85.2% and 65.1% adsorption amounts decrease are calculated for resin ND-1 and ND-3 by the negative influence of 1 mmol L -1 NaCl. This weaken effect of organic acid is generally depends on its hydrophobicity (Log Kow) for carboxylic acid and its ionization degree (pKb) for sulfonic acid. The resins could be reused with the slightly decreases by 1.9%, 3.2% and 5.4% after 7 cycles of regeneration, respectively for ND-1, ND-2 and ND-3, suggesting the ion exchange resin with larger pores are against its reuse by the brine solution regeneration. Copyright © 2017 Elsevier Ltd. All rights reserved.

Sorption behavior of 17 phthalic acid esters on three soils: effects of pH and dissolved organic matter, sorption coefficient measurement and QSPR study.

PubMed

Yang, Fen; Wang, Meng; Wang, Zunyao

2013-09-01

This work studies the sorption behaviors of phthalic acid esters (PAEs) on three soils by batch equilibration experiments and quantitative structure property relationship (QSPR) methodology. Firstly, the effects of soil type, dissolved organic matter and pH on the sorption of four PAEs (DMP, DEP, DAP, DBP) are investigated. The results indicate that the soil organic carbon content has a crucial influence on sorption progress. In addition, a negative correlation between pH values and the sorption capacities was found for these four PAEs. However, the effect of DOM on PAEs sorption may be more complicated. The sorption of four PAEs was promoted by low concentrations of DOM, while, in the case of high concentrations, the influence of DOM on the sorption was complicated. Then the organic carbon content normalized sorption coefficient (logKoc) values of 17 PAEs on three soils were measured, and the mean values ranged from 1.50 to 7.57. The logKoc values showed good correlation with the corresponding logKow values. Finally, two QSPR models were developed with 13 theoretical parameters to get reliable logKoc predictions. The leave-one-out cross validation (CV-LOO) indicated that the internal predictive power of the two models was satisfactory. Crown Copyright © 2013. Published by Elsevier Ltd. All rights reserved.

Long-term bioconcentration kinetics of hydrophobic chemicals in Selenastrum capricornutum and Microcystis aeruginosa

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

Koelmans, A.A.; Woude, H. van der; Hattink, J.

1999-06-01

The bioconcentration of two chlorobenzenes (CBs) and of seven polychlorobiphenyls (PCBs) to Selenastrum capricornutum and Microcystis aeruginosa was studied with accumulation experiments followed by gas purge elimination experiments. Henry's law constants at 10 C were needed to interpret the gas purge results and were measured in control experiments. For the M. aerogunisa culture, steady-state uptake was reached within days, whereas uptake by S. capricornutum took several weeks. The relationships between the log bioconcentration factors (BCF) and log octanol-water partition coefficients (K[sub OW]) were nonlinear, with relatively low values for the more hydrophobic PCBs. Rate constants for the elimination of CBsmore » and PCBs from the algal cells were shown to be larger than 1 per day when calculated with a one-compartment model. With such large rate constants, it is unlikely that the curvature observed for these species is caused by slow kinetics or that algal growth affects BCF by dilution of CB or PCB concentrations. The log BCF-log K[sub OW] relationships could be described by a simple three-phase model that accounted for the binding of CBs and PCBs to dissolved organic carbon (DOC). Modeling bioconcentration of hydrophobic chemicals in phytoplankton should account for the binding to DOC.« less

INFLUENCE OF ORGANIC COSOLVENTS ON THE SORPTION KINETICS OF HYDROPHOBIC ORGANIC CHEMICALS

EPA Science Inventory

A quantitative examination of the kinetics of sorption of hydrophobic organic chemicals by soils from mixed solvents reveals that the reverse sorption rate constant (k2) increases log-linearly with increasing volume fraction of organic cosolvent (fc). This relationship was expec...

Control of Attachment of Pseudomonas aeruginosa and Burkholderia cepacia to Surfaces by Shear Force.

PubMed

Hui, Yew Woh; Narayanan, Kumaran; Dykes, Gary A

2016-11-01

  The effect of physical shearing on the attachment of six Pseudomonas aeruginosa strains and six Burkholderia cepacia strains to glass, stainless steel, polystyrene and Teflon® was determined. A significant (p < 0.05) decrease in hydrophobicity was apparent for all P. aeruginosa strains (17-36%) and B. cepacia, MS 5 (20%) after shearing. A significant (p < 0.05) decrease in attachment of some P. aeruginosa (0.2-0.5 log CFU/cm2) and B. cepacia (0.2-0.4 log CFU/cm2) strains to some surface types was apparent after shearing. Significant (p < 0.05) correlation was observed for both numbers of flagellated cells and hydrophobicity against attachment to glass, stainless steel and polystyrene for P. aeruginosa while only hydrophobicity showed significant correlation against the same surfaces for B. cepacia. Scanning electron microscopy and protein analysis showed that shearing removed surface proteins from the cells and may have led to the observed changes in hydrophobicity and attachment to abiotic surfaces.

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.

Determination of the partition coefficient between dissolved organic carbon and seawater using differential equilibrium kinetics.

PubMed

Kim, Du Yung; Kwon, Jung-Hwan

2018-05-04

Because the freely dissolved fraction of highly hydrophobic organic chemicals is bioavailable, knowing the partition coefficient between dissolved organic carbon and water (K DOCw ) is crucial to estimate the freely dissolved fraction from the total concentration. A kinetic method was developed to obtain K DOCw that required a shorter experimental time than equilibrium methods. The equilibrium partition coefficients of four polychlorinated biphenyls (PCBs) (2,4,4'-trichlorobiphenyl (PCB 28), 2,2',3,5'-tetrachlorobiphenyl (PCB 44), 2,2',4,5,5'-pentachlorobiphenyl (PCB 101), and 2,2',4,4',5,5'-hexachlorobiphenyl (PCB 153)) between dissolved organic carbon and seawater (K DOCsw ) were determined using seawater samples from the Korean coast. The log K DOCsw values of PCB 28 were measured by equilibrating PCB 28, the least hydrophobic congener, with seawater samples, and the values ranged from 6.60 to 7.20. For the more hydrophobic PCBs (PCB 44, PCB 101, and PCB 153), kinetic experiments were conducted to determine the sorption rate constants (k 2 ) and their log K DOCsw values were obtained by comparing their k 2 with that of PCB 28. The calculated log K DOCsw values were 6.57-7.35 for PCB 44, 6.23-7.44 for PCB 101, and 6.35-7.73 for PCB 153. The validity of the proposed method was further confirmed using three less hydrophobic polycyclic aromatic hydrocarbons. This kinetic method shortened the experimental time to obtain the K DOCsw values of the more hydrophobic PCBs, which did not reach phase equilibrium. Copyright © 2018 Elsevier Ltd. All rights reserved.

Temperature dependencies of Henry's law constants and octanol/water partition coefficients for key plant volatile monoterpenoids.

PubMed

Copolovici, Lucian O; Niinemets, Ulo

2005-12-01

To model the emission dynamics and changes in fractional composition of monoterpenoids from plant leaves, temperature dependencies of equilibrium coefficients must be known. Henry's law constants (H(pc), Pa m3 mol(-1) and octanol/water partition coefficients (K(OW), mol mol(-1)) were determined for 10 important plant monoterpenes at physiological temperature ranges (25-50 degrees C for H(pc) and 20-50 degrees C for K(OW)). A standard EPICS procedure was established to determine H(pc) and a shake flask method was used for the measurements of K(OW). The enthalpy of volatilization (deltaH(vol)) varied from 18.0 to 44.3 kJ mol(-1) among the monoterpenes, corresponding to a range of temperature-dependent increase in H(pc) between 1.3- and 1.8-fold per 10 degrees C rise in temperature. The enthalpy of water-octanol phase change varied from -11.0 to -23.8 kJ mol(-1), corresponding to a decrease of K(OW) between 1.15- and 1.32-fold per 10 degrees C increase in temperature. Correlations among physico-chemical characteristics of a wide range of monoterpenes were analyzed to seek the ways of derivation of H(pc) and K(OW) values from other monoterpene physico-chemical characteristics. H(pc) was strongly correlated with monoterpene saturated vapor pressure (P(v)), and for lipophilic monoterpenes, deltaH(vol) scaled positively with the enthalpy of vaporization that characterizes the temperature dependence of P(v) Thus, P(v) versus temperature relations may be employed to derive the temperature relations of H(pc) for these monoterpenes. These data collectively indicate that monoterpene differences in H(pc) and K(OW) temperature relations can importantly modify monoterpene emissions from and deposition on plant leaves.

Surface characteristics of Bacillus cereus and its adhesion to stainless steel.

PubMed

Peng, J S; Tsai, W C; Chou, C C

2001-04-11

The ability of a Bacillus cereus strain, isolated from spoiled milk, to adhere to the surface of stainless steel chips was evaluated during its growth in diluted tryptic soy broth (DTSB). The number of cells that adhered to the surface increased markedly as the culture reached the end of the log phase and entered stationary phase, and continued to increase with further incubation. The surface properties of cells from the log, stationary, and late stationary phases were measured by hydrophobic interaction chromatography (HIC) and electrostatic interaction chromatography (ESIC). It was found that surface hydrophobicity of B. cereus vegetative cells from the late stationary phase was the highest followed by those from the stationary phase and the log phase cultures. While the vegetative cells prepared from stationary phase and log phase cultures, respectively, had the highest and the lowest surface charges. Adhesion of B. cereus vegetative cells to stainless steel was positively correlated with the cell surface hydrophobicity (R = 0.979). Surface hydrophobicity and surface positive charge noted on the spores harvested from diluted tryptic soy agar (DTSA) and Mn2+-tryptone glucose extract agar were higher than those harvested from the sucrose or lactose-added DTSA. A wide variation in the surface charge values was noted on the surface of various spores prepared from cultures grown on the four different media tested, while their ability to adhere to stainless steel chips in phosphate buffered saline (PBS) showed no significant difference (p > 0.05). Similarly, the number of spores or vegetative cells adhering to stainless steel suspended in PBS, milk or diluted milk (1000 x) did not differ significantly (p > 0.05).

Predicting the bioconcentration factor of highly hydrophobic organic chemicals.

PubMed

Garg, Rajni; Smith, Carr J

2014-07-01

Bioconcentration refers to the process of uptake and buildup of chemicals in living organisms. Experimental measurement of bioconcentration factor (BCF) is time-consuming and expensive, and is not feasible for a large number of chemicals of regulatory concern. Quantitative structure-activity relationship (QSAR) models are used for estimating BCF values to help in risk assessment of a chemical. This paper presents the results of a QSAR study conducted to address an important problem encountered in the prediction of the BCF of highly hydrophobic chemicals. A new QSAR model is derived using a dataset of diverse organic chemicals previously tested in a United States Environmental Protection Agency laboratory. It is noted that the linear relationship between the BCF and hydrophobic parameter, i.e., calculated octanol-water partition coefficient (ClogP), breaks down for highly hydrophobic chemicals. The parabolic QSAR equation, log BCF=3.036 ClogP-0.197 ClogP(2)-0.808 MgVol (n=28, r(2)=0.817, q(2)=0.761, s=0.558) (experimental log BCF range=0.44-5.29, ClogP range=3.16-11.27), suggests that a non-linear relationship between BCF and the hydrophobic parameter, along with inclusion of additional molecular size, weight and/or volume parameters, should be considered while developing a QSAR model for more reliable prediction of the BCF of highly hydrophobic chemicals. Copyright © 2014 The Authors. Published by Elsevier Ltd.. All rights reserved.

Effect of hydrophobicity of pharmaceuticals and personal care products for adsorption on activated carbon: Adsorption isotherms, kinetics and mechanism.

PubMed

Kaur, Harkirat; Bansiwal, Amit; Hippargi, Girivyankatesh; Pophali, Girish R

2017-09-11

Adsorption of three pharmaceuticals and personal care products (PPCPs), namely caffeine, ibuprofen and triclosan on commercial powdered activated carbon was examined in aqueous medium. The contaminants were chosen based on their diverse log K ow (octanol-water partition coefficient) viz. - 0.07 for caffeine, 3.97 for ibuprofen and 4.76 for triclosan to examine the role of hydrophobicity on adsorption process. The adsorbent characterisation was achieved using BET surface area, SEM, pore size distribution studies and FTIR. Influence of mass of PAC, contact time, solution pH and initial concentration on adsorption capacity of PAC was studied. Adsorption isotherms and kinetics were applied to establish the mechanism of adsorption. The kinetics followed pseudo-second order with physisorption occurring through particle diffusion. The Freundlich model fitted best among the isotherm models. The adsorption capacity increased in the order CFN < IBU < TCS which correlates with increasing hydrophobicity (log K ow ), molecular weight and decreasing water solubility, respectively. We conclude that micro-pollutant hydrophobicity contributes towards adsorption on activated carbon.

The binding of orally dosed hydrophobic active pharmaceutical ingredients to casein micelles in milk.

PubMed

Cheema, M; Hristov, A N; Harte, F M

2017-11-01

Casein proteins (α S1 -, α S2 -, β- and κ-casein) account for 80% of the total protein content in bovine milk and form casein micelles (average diameter = 130 nm, approximately 10 15 micelles/mL). The affinity of native casein micelles with the 3 hydrophobic active pharmaceutical ingredients (API), meloxicam [351.4 g/mol; log P = 3.43; acid dissociation constant (pK a ) = 4.08], flunixin (296.2 g/mol; log P = 4.1; pK a = 5.82), and thiabendazole (201.2 g/mol; log P = 2.92; pK a = 4.64), was evaluated in bovine milk collected from dosed Holstein cows. Native casein micelles were separated from raw bovine milk by mild techniques such as ultracentrifugation, diafiltration, isoelectric point precipitation (pH 4.6), and size exclusion chromatography. Acetonitrile extraction of hydrophobic API was then done, followed by quantification using HPLC-UV. For the API or metabolites meloxicam, 5-hyroxy flunixin and 5-hydroxy thiabendazole, 31 ± 3.90, 31 ± 1.3, and 28 ± 0.5% of the content in milk was associated with casein micelles, respectively. Less than ∼5.0% of the recovered hydrophobic API were found in the milk fat fraction, and the remaining ∼65% were associated with the whey/serum fraction. A separate in vitro study showed that 66 ± 6.4% of meloxicam, 29 ± 0.58% of flunixin, 34 ± 0.21% of the metabolite 5-hyroxy flunixin, 50 ± 4.5% of thiabendazole, and 33 ± 3.8% of metabolite 5-hydroxy thiabendazole was found partitioned into casein micelles. Our study supports the hypothesis that casein micelles are native carriers for hydrophobic compounds in bovine milk. Copyright © 2017 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

High-throughput determination of octanol/water partition coefficients using a shake-flask method and novel two-phase solvent system.

PubMed

Morikawa, Go; Suzuka, Chihiro; Shoji, Atsushi; Shibusawa, Yoichi; Yanagida, Akio

2016-01-05

A high-throughput method for determining the octanol/water partition coefficient (P(o/w)) of a large variety of compounds exhibiting a wide range in hydrophobicity was established. The method combines a simple shake-flask method with a novel two-phase solvent system comprising an acetonitrile-phosphate buffer (0.1 M, pH 7.4)-1-octanol (25:25:4, v/v/v; AN system). The AN system partition coefficients (K(AN)) of 51 standard compounds for which log P(o/w) (at pH 7.4; log D) values had been reported were determined by single two-phase partitioning in test tubes, followed by measurement of the solute concentration in both phases using an automatic flow injection-ultraviolet detection system. The log K(AN) values were closely related to reported log D values, and the relationship could be expressed by the following linear regression equation: log D=2.8630 log K(AN) -0.1497(n=51). The relationship reveals that log D values (+8 to -8) for a large variety of highly hydrophobic and/or hydrophilic compounds can be estimated indirectly from the narrow range of log K(AN) values (+3 to -3) determined using the present method. Furthermore, log K(AN) values for highly polar compounds for which no log D values have been reported, such as amino acids, peptides, proteins, nucleosides, and nucleotides, can be estimated using the present method. The wide-ranging log D values (+5.9 to -7.5) of these molecules were estimated for the first time from their log K(AN) values and the above regression equation. Copyright © 2015 Elsevier B.V. All rights reserved.

Mathematical relationships between metrics of chemical bioaccumulation in fish.

PubMed

Mackay, Don; Arnot, Jon A; Gobas, Frank A P C; Powell, David E

2013-07-01

Five widely used metrics of bioaccumulation in fish are defined and discussed, namely the octanol-water partition coefficient (KOW ), bioconcentration factor (BCF), bioaccumulation factor (BAF), biomagnification factor (BMF), and trophic magnification factor (TMF). Algebraic relationships between these metrics are developed and discussed using conventional expressions for chemical uptake from water and food and first-order losses by respiration, egestion, biotransformation, and growth dilution. Two BCFs may be defined, namely as an equilibrium partition coefficient KFW or as a nonequilibrium BCFK in which egestion losses are included. Bioaccumulation factors are shown to be the product of the BCFK and a novel equilibrium multiplier M containing 2 ratios, namely, the diet-to-water concentration ratio and the ratio of uptake rate constants for respiration and dietary uptake. Biomagnification factors are shown to be proportional to the lipid-normalized ratio of the predator/prey values of BCFK and the ratio of the equilibrium multipliers. Relationships with TMFs are also discussed. The effects of chemical hydrophobicity, biotransformation, and growth are evaluated by applying the relationships to a range of illustrative chemicals of varying KOW in a linear 4-trophic-level food web with typical values for uptake and loss rate constants. The roles of respiratory and dietary intakes are demonstrated, and even slow rates of biotransformation and growth can significantly affect bioaccumulation. The BCFK s and the values of M can be regarded as the fundamental determinants of bioaccumulation and biomagnification in aquatic food webs. Analyzing data from food webs can be enhanced by plotting logarithmic lipid-normalized concentrations or fugacities as a linear function of trophic level to deduce TMFs. Implications for determining bioaccumulation by laboratory tests for regulatory purposes are discussed. Copyright © 2013 SETAC.

Bioaccumulation of polycyclic aromatic compounds: 2. Modeling bioaccumulation in marine organisms chronically exposed to dispersed oil.

PubMed

Baussant, T; Sanni, S; Skadsheim, A; Jonsson, G; Børseth, J F; Gaudebert, B

2001-06-01

Within the frame of a large environmental study, we report on a research program that investigated the potential for bioaccumulation and subsequent effect responses in several marine organisms exposed to chronic levels of dispersed crude oil. Body burden can be estimated from kinetic parameters (rate constants for uptake and elimination), and appropriate body burden-effect relationships may improve assessments of environmental risks or the potential for such outcomes following chronic discharges at sea. We conducted a series of experiments in a flow-through system to describe the bioaccumulation kinetics of polycyclic aromatic hydrocarbons (PAH) at low concentrations of dispersed crude oils. Mussels (Mytilus edulis) and juvenile turbot (Scophthalmus maximus) were exposed for periods ranging from 8 to 21 d. Postexposure, the organisms were kept for a period of 9 to 10 d in running seawater to study elimination processes. Rate constants of uptake (k1) and elimination (k2) of the PAHs during and following exposure were calculated using a first-order kinetic model that assumed a decrease of the substances in the environment over time. The estimated bioconcentration factor was calculated from the ratio of k1/k2. The kinetic parameters of two-, three-, and four-ring PAHs in mussel and fish are compared with estimates based on hydrophobicity alone, expressed by the octanol-water partition coefficient, Kow (partitioning theory). A combination of reduced bioavailability of PAHs from oil droplets and degradation processes of PAHs in body tissues seems to explain discrepancies between kinetic rates based on Kow and actual kinetic rates measured in fish. Mussels showed a pattern more in compliance with the partitioning theory.

Linear solvation energy relationships regarding sorption and retention properties of hydrophobic organic compounds in soil leaching column chromatography.

PubMed

Xu, Feng; Liang, Xinmiao; Lin, Bingcheng; Su, Fan; Schramm, Karl-Werner; Kettrup, Antonius

2002-08-01

The capacity factors of a series of hydrophobic organic compounds (HOCs) were measured in soil leaching column chromatography (SLCC) on a soil column, and in reversed-phase liquid chromatography on a C18 column with different volumetric fractions (phi) of methanol in methanol-water mixtures. A general equation of linear solvation energy relationships, log(XYZ) XYZ0 + mV(I)/100 + spi + bbetam + aalpham, was applied to analyze capacity factors (k'), soil organic partition coefficients (Koc) and octanol-water partition coefficients (P). The analyses exhibited high accuracy. The chief solute factors that control logKoc, log P, and logk' (on soil and on C18) are the solute size (V(I)/100) and hydrogen-bond basicity (betam). Less important solute factors are the dipolarity/polarizability (pi*) and hydrogen-bond acidity (alpham). Log k' on soil and log Koc have similar signs in four fitting coefficients (m, s, b and a) and similar ratios (m:s:b:a), while log k' on C18 and logP have similar signs in coefficients (m, s, b and a) and similar ratios (m:s:b:a). Consequently, logk' values on C18 have good correlations with logP (r > 0.97), while logk' values on soil have good correlations with logKoc (r > 0.98). Two Koc estimation methods were developed, one through solute solvatochromic parameters, and the other through correlations with k' on soil. For HOCs, a linear relationship between logarithmic capacity factor and methanol composition in methanol-water mixtures could also be derived in SLCC.

Ubiquitin fusion constructs allow the expression and purification of multi-KOW domain complexes of the Saccharomyces cerevisiae transcription elongation factor Spt4/5.

PubMed

Blythe, Amanda; Gunasekara, Sanjika; Walshe, James; Mackay, Joel P; Hartzog, Grant A; Vrielink, Alice

2014-08-01

Spt4/5 is a hetero-dimeric transcription elongation factor that can both inhibit and promote transcription elongation by RNA polymerase II (RNAPII). However, Spt4/5's mechanism of action remains elusive. Spt5 is an essential protein and the only universally-conserved RNAP-associated transcription elongation factor. The protein contains multiple Kyrpides, Ouzounis and Woese (KOW) domains. These domains, in other proteins, are thought to bind RNA although there is little direct evidence in the literature to support such a function in Spt5. This could be due, at least in part, to difficulties in expressing and purifying recombinant Spt5. When expressed in Escherichia coli (E. coli), Spt5 is innately insoluble. Here we report a new approach for the successful expression and purification of milligram quantities of three different multi-KOW domain complexes of Saccharomyces cerevisiae Spt4/5 for use in future functional studies. Using the E. coli strain Rosetta2 (DE3) we have developed strategies for co-expression of Spt4 and multi-KOW domain Spt5 complexes from the bi-cistronic pET-Duet vector. In a second strategy, Spt4/5 was expressed via co-transformation of Spt4 in the vector pET-M11 with Spt5 ubiquitin fusion constructs in the vector pHUE. We characterized the multi-KOW domain Spt4/5 complexes by Western blot, limited proteolysis, circular dichroism, SDS-PAGE and size exclusion chromatography-multiangle light scattering and found that the proteins are folded with a Spt4:Spt5 hetero-dimeric stoichiometry of 1:1. These expression constructs encompass a larger region of Spt5 than has previously been reported, and will provide the opportunity to elucidate the biological function of the multi-KOW containing Spt5. Copyright © 2014 Elsevier Inc. All rights reserved.

Evaluation of the artificial membrane permeability of drugs by digital simulation.

PubMed

Nakamura, Mayumi; Osakai, Toshiyuki

2016-08-25

A digital simulation method has been developed for evaluating the membrane permeability of drugs in the parallel artificial membrane permeation assay (PAMPA). The simulation results have shown that the permeability coefficient (log Ppampa) of drugs is linearly increased with increasing their distribution coefficient (log KD,M) to the lipid membrane, i.e., the hydrophobicity of the drug molecules. However, log Ppampa shows signs of leveling off for highly hydrophobic drugs. Such a dependence of log Ppampa is in harmony with the reported experimental data, and has been well explained in terms of the change in the rate-determining step from the diffusion in the membrane to that in the unstirred water layer (UWL) on both sides of the membrane. Additionally, the effects of several factors, including lag time, diffusion coefficient, pH, and pKa, on the permeability coefficient have been well simulated. It has thus been suggested that the proposed method should be promising for in silico evaluation of the membrane permeability of drugs. Copyright © 2016 Elsevier B.V. All rights reserved.

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.

Quantitative structure activity relationship and risk analysis of some pesticides in the goat milk.

PubMed

Muhammad, Faqir; Awais, Mian Muhammad; Akhtar, Masood; Anwar, Muhammad Irfan

2013-01-04

The detection and quantification of different pesticides in the goat milk samples collected from different localities of Faisalabad, Pakistan was performed by HPLC using solid phase microextraction. The analysis showed that about 50% milk samples were contaminated with pesticides. The mean±SEM levels (ppm) of cyhalothrin, endosulfan, chlorpyrifos and cypermethrin were 0.34±0.007, 0.063±0.002, 0.034±0.002 and 0.092±0.002, respectively; whereas, methyl parathion was not detected in any of the analyzed samples. Quantitative structure activity relationship (QSAR) models were suggested to predict the residues of unknown pesticides in the goat milk using their known physicochemical characteristics including molecular weight (MW), melting point (MP), and log octanol to water partition coefficient (Ko/w) in relation to the characteristics such as pH, % fat, specific gravity and refractive index of goat milk. The analysis revealed good correlation coefficient (R2 = 0.985) for goat QSAR model. The coefficients for Ko/w and refractive index for the studied pesticides were higher in goat milk. This suggests that these are better determinants for pesticide residue prediction in the milk of these animals. Based upon the determined pesticide residues and their provisional tolerable daily intakes, risk analysis was also conducted which showed that daily intake levels of pesticide residues including cyhalothrin, chlorpyrifos and cypermethrin in present study are 2.68, 5.19 and 2.71 times higher, respectively in the goat milk. This intake of pesticide contaminated milk might pose health hazards to humans in this locality.

Quantitative structure activity relationship and risk analysis of some pesticides in the goat milk

PubMed Central

2013-01-01

The detection and quantification of different pesticides in the goat milk samples collected from different localities of Faisalabad, Pakistan was performed by HPLC using solid phase microextraction. The analysis showed that about 50% milk samples were contaminated with pesticides. The mean±SEM levels (ppm) of cyhalothrin, endosulfan, chlorpyrifos and cypermethrin were 0.34±0.007, 0.063±0.002, 0.034±0.002 and 0.092±0.002, respectively; whereas, methyl parathion was not detected in any of the analyzed samples. Quantitative structure activity relationship (QSAR) models were suggested to predict the residues of unknown pesticides in the goat milk using their known physicochemical characteristics including molecular weight (MW), melting point (MP), and log octanol to water partition coefficient (Ko/w) in relation to the characteristics such as pH, % fat, specific gravity and refractive index of goat milk. The analysis revealed good correlation coefficient (R2 = 0.985) for goat QSAR model. The coefficients for Ko/w and refractive index for the studied pesticides were higher in goat milk. This suggests that these are better determinants for pesticide residue prediction in the milk of these animals. Based upon the determined pesticide residues and their provisional tolerable daily intakes, risk analysis was also conducted which showed that daily intake levels of pesticide residues including cyhalothrin, chlorpyrifos and cypermethrin in present study are 2.68, 5.19 and 2.71 times higher, respectively in the goat milk. This intake of pesticide contaminated milk might pose health hazards to humans in this locality. PMID:23369514

The effect of suspended particles coated by humic acid on the toxicity of pharmaceuticals, estrogens, and phenolic compounds.

PubMed

Ra, Jin Sung; Oh, Seok-Young; Lee, Byung Cheun; Kim, Sang Don

2008-02-01

The sorption characteristics of 10 organic chemicals, categorized as pharmaceuticals, estrogens and phenols, onto synthetic suspended particle (i.e., alumina) coated with humic acid were investigated according to their octanol-water partition coefficient (K(ow)). Chemical analyses were performed with gas chromatography and mass spectrometry (GC/MS) and high performance liquid chromatography (HPLC). The effects of particles on the toxicity reduction were evaluated using bioassay tests, using Daphnia magna and Vibrio fisheri for phenols and pharmaceuticals, and the human breast cancer cell MCF-7 for estrogens. Sorption studies revealed that 22 and 38% of octylphenol and pentachlorophenol, respectively, were removed by suspended particle, whereas 2,4-dichlorophenol was not removed, which was directly proportional to the logK(ow) value. Similar to the sorption tests, suspended particles significantly reduced the acute toxicities of octylphenol and pentachlorophenol to D. magna and V. fisheri (p<0.01), but there was no significant difference in the toxicity of 2,4-dichlorophenol to D. magna (p=0.8374). Pharmaceuticals, such as ibuprofen, gemfibrozil and tolfenamic acid, showed no discernible sorption to the suspended particle, with the exception of diclofenac, which revealed 11% sorption. For estrogens, such as estrone, 17beta-estradiol and 17alpha-ethynylestradiol, the results indicated no reduction in the sorption test. This may be attributed to the polar interaction by functional groups in sorption between pharmaceuticals and estrogens and suspended particles. In the bioassays, presence of suspended particles did not significantly modify the toxicity of pharmaceuticals (regardless of their K(ow) values) to D. magna, V. fisheri or E-screen.

Electroporation enhances antimicrobial photodynamic therapy mediated by the hydrophobic photosensitizer, hypericin, Electroporation enhances antimicrobial photodynamic inactivation

PubMed Central

de Melo, Wanessa de Cássia Martins Antunes; Lee, Alexander N; Perussi, Janice Rodrigues; Hamblin, Michael R.

2013-01-01

The effective transport of photosensitizers (PS) across the membrane and the intracellular accumulation of PS are the most crucial elements in antimicrobial photodynamic therapy (aPDT). However, due to the morphological complexity of Gram-negative bacteria the penetration of PS is limited, especially hydrophobic PS. Electroporation (EP) could increase the effectiveness of aPDT, by promoting the formation of transient pores that enhance the permeability of the bacterial membrane to PS. In this study we evaluated the combination of aPDT mediated by the hydrophobic PS, hypericin and EP (aPDT/EP) against Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli. These bacteria were exposed to light (590 nm) in the presence of hypericin (4µM), following electroporation. The results showed that aPDT/EP inactivated 3.67 logs more E. coli and 2.65 logs more S. aureus than aPDT alone. Based on these results we suggest that EP can potentiate the aPDT effect. PMID:24284122

Comparison of polymer induced and solvent induced trypsin denaturation: the role of hydrophobicity.

PubMed

Jasti, Lakshmi S; Fadnavis, Nitin W; Addepally, Uma; Daniels, Siona; Deokar, Sarika; Ponrathnam, Surendra

2014-04-01

Trypsin adsorption from aqueous buffer by various copolymers of allyl glycidyl ether-ethylene glycol dimethacrylate (AGE-EGDM) copolymer with varying crosslink density increases with increasing crosslink density and the effect slowly wears off after reaching a plateau at 50% crosslink density. The copolymer with 25% crosslink density was reacted with different amines with alkyl/aryl side chains to obtain a series of copolymers with 1,2-amino alcohol functional groups and varying hydrophobicity. Trypsin binding capacity again increases with hydrophobicity of the reacting amine and a good correlation between logPoctanol of the amine and protein binding is observed. The bound trypsin is denatured to the extent of 90% in spite of the presence of hydrophilic hydroxyl and amino groups. The behavior was comparable to that in mixtures of aqueous buffer and water-miscible organic co-solvents where the solvent concentration required to deactivate 50% of the enzyme (C50) is dependent on logPoctanol of the co-solvent. Copyright © 2014 Elsevier B.V. All rights reserved.

Partition coefficients of organic compounds in lipid-water systems and correlations with fish bioconcentration factors

USGS Publications Warehouse

Chiou, C.T.

1985-01-01

Triolein-water partition coefficients (KtW) have been determined for 38 slightly water-soluble organic compounds, and their magnitudes have been compared with the corresponding octanol-water partition coefficients (KOW). In the absence of major solvent-solute interaction effects in the organic solvent phase, the conventional treatment (based on Raoult's law) predicts sharply lower partition coefficients for most of the solutes in triolein because of its considerably higher molecular weight, whereas the Flory-Huggins treatment predicts higher partition coefficients with triolein. The data are in much better agreement with the Flory-Huggins model. As expected from the similarity in the partition coefficients, the water solubility (which was previously found to be the major determinant of the KOW) is also the major determinant for the Ktw. When the published BCF values (bioconcentration factors) of organic compounds in fish are based on the lipid content rather than on total mass, they are approximately equal to the Ktw, which suggests at least near equilibrium for solute partitioning between water and fish lipid. The close correlation between Ktw and Kow suggests that Kow is also a good predictor for lipid-water partition coefficients and bioconcentration factors.

Fate of pharmaceutical compounds in hydroponic mesocosms planted with Scirpus validus.

PubMed

Zhang, Dong Qing; Gersberg, Richard M; Hua, Tao; Zhu, Junfei; Goyal, Manish Kumar; Ng, Wun Jern; Tan, Soon Keat

2013-10-01

A systematic approach to assess the fate of selected pharmaceuticals (carbamazepine, naproxen, diclofenac, clofibric acid and caffeine) in hydroponic mesocosms is described. The overall objective was to determine the kinetics of depletion (from solution) and plant uptake for these compounds in mesocosms planted with S. validus growing hydroponically. The potential for translocation of these pharmaceuticals from the roots to the shoots was also assessed. After 21 days of incubation, nearly all of the caffeine, naproxen and diclofenac were eliminated from solution, whereas carbamazepine and clofibric acid were recalcitrant to both photodegradation and biodegradation. The fact that the BAFs for roots for carbamazepine and clofibric acid were greater than 5, while the BAFs for naproxen, diclofenac and caffeine were less than 5, implied that the latter two compounds although recalcitrant to biodegradation, still had relatively high potential for plant uptake. Naproxen was sensitive to both photodegradation (30-42%) and biodegradation (>50%), while diclofenac was particularly sensitive (>70%) to photodegradation alone. No significant correlations (p > 0.05) were found between the rate constants of depletion or plant tissue levels of the pharmaceuticals and either log Kow or log Dow. Copyright © 2013 Elsevier Ltd. All rights reserved.

Sorption and biodegradation of artificial sweeteners in activated sludge processes.

PubMed

Tran, Ngoc Han; Gan, Jie; Nguyen, Viet Tung; Chen, Huiting; You, Luhua; Duarah, Ankur; Zhang, Lifeng; Gin, Karina Yew-Hoong

2015-12-01

There is limited information on the occurrence and removal of artificial sweeteners (ASs) in biological wastewater treatment plants, and in particular, the contribution of sorption and biodegradation to their removal. This study investigated the fate of ASs in both the aqueous and solid phases in a water reclamation plant (WRP). All the four targeted ASs, i.e. acesulfame (ACE), sucralose (SUC), cyclamate (CYC) and saccharine (SAC), were detected in both the aqueous and solid phases of raw influent and primary effluent samples. The concentrations of CYC and SAC in secondary effluent or MBR permeate were below their method detection limits. ACE and SUC were persistent throughout the WRP, whereas CYC and SAC were completely removed in biological treatment (>99%). Experimental results showed that sorption played a minor role in the elimination of the ASs due to the relatively low sorption coefficients (Kd), where Kd<500L/kg. In particular, the poor removal of ACE and SUC in the WRP may be attributed to their physiochemical properties (i.e. logKow<0 or logD<3.2) and chemical structures containing strong withdrawing electron functional groups in heterocyclic rings (i.e. chloride and sulfonate). Copyright © 2015 Elsevier Ltd. All rights reserved.

Determination and theoretical aspects of the equilibrium between dissolved organic matter and hydrophobic organic micropollutants in water (Kdoc).

PubMed

Krop, H B; van Noort, P C; Govers, H A

2001-01-01

Literature on the equilibrium constant for distribution between dissolved organic carbon (DOC) (Kdoc) data of strongly hydrophobic organic contaminants were collected and critically analyzed. About 900 Kdoc entries for experimental values were retrieved and tabulated, including those factors that can influence them. In addition, quantitative structure-activity relationship (QSAR) prediction equations were retrieved and tabulated. Whether a partition or association process between the contaminant and DOC takes place could not be fully established, but indications toward an association process are strong in several cases. Equilibrium between a contaminant and DOC in solution was shown to be achieved within a minute. When the equilibrium shifts in time, this was caused by either a physical or chemical change of the DOC, affecting the lighter fractions most. Adsorption isotherms turned out to be linear in the contaminant concentration for the relevant DOC concentration up to 100 mg of C/L. Eighteen experimental methods have been developed for the determination of the pertinent distribution constant. Experimental Kdoc values revealed the expected high correlation with partition coefficients over n-octanol and water (Kow) for all experimental methods, except for the HPLC and apparent solubility (AS) method. Only fluorescence quenching (FQ) and solid-phase microextraction (SPME) methods could quantify fast equilibration. Only 21% of the experimental values had a 95% confidence interval, which was statistically significantly different from zero. Variation in Kdoc values was shown to be high, caused mainly by the large variation of DOC in water samples. Even DOC from one sample gave different equilibrium constants for different DOC fractions. Measured Kdoc values should, therefore, be regarded as average values. Kdoc was shown to increase on increasing molecular mass, indicating that the molecular mass distribution is a proper normalization function for the average Kdoc at the current state of knowledge. The weakly bound fraction could easily be desorbed when other adsorbing media, such as a SepPak column or living organism, are present. The amount that moves from the DOC to the other medium will depend, among other reasons, on the size of the labile DOC fraction and the equilibrium constant of the other medium. Variation of Kdoc with temperature turned out to be small, probably caused by a small enthalpy of transfer from water to DOC. Ionic strength turned out to be more important, leading to changes of a factor of 2-5. The direction of this effect depends on the type of ion. With respect to QSAR relationships between Kdoc and macroscopic or molecular descriptors, it was concluded that only a small number of equations are available in the literature, for apolar compounds only, and with poor statistics and predictive power. Therefore, a first requirement is the improvement of the availability and quality of experimental data. Along with this, theoretical (mechanistic) models for the relationship between DOC plus contaminant descriptors on the one side and Kdoc on the other should be further developed. Correlations between Kdoc and Kow and those between the soil-water partition constant (Koc) and Kow were significantly different only in the case of natural aquatic DOC, pointing at substantial differences between these two types of organic material and at a high correspondence for other types of commercial and natural DOC.

Experimental methodology for assessing the environmental fate of organic chemicals in polymer matrices using column leaching studies and OECD 308 water/sediment systems: Application to tire and road wear particles.

PubMed

Unice, Kenneth M; Bare, Jennifer L; Kreider, Marisa L; Panko, Julie M

2015-11-15

Automobile tires require functional rubber additives including curing agents and antioxidants, which are potentially environmentally available from tire and road wear particles (TRWP) deposited in soil and sediment. A novel methodology was employed to evaluate the environmental fate of three commonly-used tire chemicals (N-cyclohexylbenzothiazole-2-sulfenamide (CBS), N-(1,3-dimethylbutyl)-N'-phenyl-1,4-phenylenediamine (6-PPD) and 1,3-diphenylguanidine (DPG)), using a road simulator, an artificial weathering chamber, column leaching tests, and OECD 308 sediment/water incubator studies. Environmental release factors were quantified for curing (f(C)), tire wear (f(W)), terrestrial weathering (f(S)), leaching from TRWP (f(L)), and environmental availability from TRWP (f(A)) by liquid chromatography-tandem mass spectroscopy (LC/MS/MS) analyses. Cumulative fractions representing total environmental availability (F(T)) and release to water (FR) were calculated for the tire chemicals and 13 transformation products. F(T) for CBS, DPG and 6-PPD inclusive of transformation products for an accelerated terrestrial aging time in soil of 0.1 years was 0.08, 0.1, and 0.06, respectively (equivalent to 6 to 10% of formulated mass). In contrast, a wider range of 5.5×10(-4) (6-PPD) to 0.06 (CBS) was observed for F(R) at an accelerated age of 0.1 years, reflecting the importance of hydrophobicity and solubility for determining the release to the water phase. Significant differences (p<0.05) in the weathering factor, f(S), were observed when chemicals were categorized by boiling point or hydrolysis rate constant. A significant difference in the leaching factor, f(L), and environmental availability factor, f(A), was also observed when chemicals were categorized by log K(ow). Our methodology should be useful for lifecycle analysis of other functional polymer chemicals. Copyright © 2015 Elsevier B.V. All rights reserved.

Are styrene oligomers in coastal sediments of an industrial area aryl hydrocarbon-receptor agonists?

PubMed

Hong, Seongjin; Lee, Junghyun; Lee, Changkeun; Yoon, Seo Joon; Jeon, Seungyeon; Kwon, Bong-Oh; Lee, Jong-Hyeon; Giesy, John P; Khim, Jong Seong

2016-06-01

Effect-directed analysis (EDA) was performed to identify the major aryl hydrocarbon receptor (AhR) agonists in sediments collected from a highly industrialized area (Lake Shihwa, Korea). Great AhR-mediated potencies were found in fractions containing aromatic compounds with log Kow values of 5-8, and relatively great concentrations of styrene oligomers (SOs) and polycyclic aromatic hydrocarbons (PAHs) were detected in those fractions. Until now, there was little information on occurrences and toxic relative potencies (RePs) of SOs in coastal environments. In the present study; i) distributions and compositions, ii) AhR binding affinities, and iii) contributions of SOs to total AhR-mediated potencies were determined in coastal sediments. Elevated concentrations of 10 SOs were detected in sediments of inland creeks ranging from 61 to 740 ng g(-1) dry mass (dm), while lesser concentrations were found in inner (mean = 33 ng g(-1) dm) and outer regions (mean = 25 ng g(-1) dm) of the lake. Concentrations of PAHs in sediments were comparable to those of SOs. 2,4-diphenyl-1-butene (SD3) was the predominant SO analogue in sediments. SOs and PAHs were accumulated in sediments near sources, and could not be transported to remote regions due to their hydrophobicity. RePs of 3 SOs could be derived, which were 1000- to 10,000-fold less than that of one representative potent AhR active PAH, benzo[a]pyrene. Although concentrations of SOs in sediments were comparable to those of PAHs, the collective contribution of SOs to total AhR-mediated potencies were rather small (<1%), primarily due to their smaller RePs. Overall, the present study provides information on distributions and AhR binding affinities for SOs as baseline data for degradation products of polystyrene plastic in the coastal environment. Copyright © 2016 Elsevier Ltd. All rights reserved.

Sorption and Transport of Pharmaceutical chemicals in Organic- and Mineral-rich Soils

NASA Astrophysics Data System (ADS)

Vulava, V. M.; Schwindaman, J.; Murphey, V.; Kuzma, S.; Cory, W.

2011-12-01

Pharmaceutical, active ingredients in personal care products (PhACs), and their derivative compounds are increasingly ubiquitous in surface waters across the world. Sorption and transport of four relatively common PhACs (naproxen, ibuprofen, cetirizine, and triclosan) in different natural soils was measured. All of these compounds are relatively hydrophobic (log KOW>2) and have acid/base functional groups, including one compound that is zwitterionic (cetirizine.) The main goal of this study was to correlate organic matter (OM) and clay content in natural soils and sediment with sorption and degradation of PhACs and ultimately their potential for transport within the subsurface environment. A- and B-horizon soils were collected from four sub-regions within a pristine managed forested watershed near Charleston, SC, with no apparent sources of anthropogenic contamination. These four soil series had varying OM content (fOC) between 0.4-9%, clay mineral content between 6-20%, and soil pH between 4.5-6. The A-horizon soils had higher fOC and lower clay content than the B-horizon soils. Sorption isotherms measured from batch sorption experimental data indicated a non-linear sorption relationship in all A- and B-horizon soils - stronger sorption was observed at lower PhAC concentrations and lower sorption at higher concentrations. Three PhACs (naproxen, ibuprofen, and triclosan) sorbed more strongly with higher fOC A-horizon soils compared with the B-horizon soils. These results show that soil OM had a significant role in strongly binding these three PhACs, which had the highest KOW values. In contrast, cetirizine, which is predominantly positively charged at pH below 8, strongly sorbed to soils with higher clay mineral content and least strongly to higher fOC soils. All sorption isotherms fitted well to the Freundlich model. For naproxen, ibuprofen, and triclosan, there was a strong and positive linear correlation between the Freundlich adsorption constant, Kf, and fOC, again indicating that these PhACs preferentially partition into the soil OM. Such a correlation was absent for cetirizine. Breakthrough curves of PhACs measured in homogeneous packed soil columns indicated that PhAC transport was affected by chemical nonequilibrium processes depending on the soil and PhAC chemistry. The shape of the breakthrough curves indicated that there were two distinct sorption sites - OM and clay minerals - which influence nonequilibrium transport of these compounds. The retardation factor estimated using the distribution coefficient, Kd, measured from the sorption experiments was very similar to the measured value. While the sorption and transport data do not provide mechanistic information regarding the nature of PhAC interaction with chemical reactive components within geological materials, they do provide important information regarding potential fate of such compounds in the environment. The results also show the role that soil OM and mineral surfaces play in sequestering or transporting these chemicals. These insights have implications to the quality of the water resources in our communities.

Quantitative structure-activity relationship for the partition coefficient of hydrophobic compounds between silicone oil and air.

PubMed

Qu, Yanfei; Ma, Yongwen; Wan, Jinquan; Wang, Yan

2018-06-01

The silicon oil-air partition coefficients (K SiO/A ) of hydrophobic compounds are vital parameters for applying silicone oil as non-aqueous-phase liquid in partitioning bioreactors. Due to the limited number of K SiO/A values determined by experiment for hydrophobic compounds, there is an urgent need to model the K SiO/A values for unknown chemicals. In the present study, we developed a universal quantitative structure-activity relationship (QSAR) model using a sequential approach with macro-constitutional and micromolecular descriptors for silicone oil-air partition coefficients (K SiO/A ) of hydrophobic compounds with large structural variance. The geometry optimization and vibrational frequencies of each chemical were calculated using the hybrid density functional theory at the B3LYP/6-311G** level. Several quantum chemical parameters that reflect various intermolecular interactions as well as hydrophobicity were selected to develop QSAR model. The result indicates that a regression model derived from logK SiO/A , the number of non-hydrogen atoms (#nonHatoms) and energy gap of E LUMO and E HOMO (E LUMO -E HOMO ) could explain the partitioning mechanism of hydrophobic compounds between silicone oil and air. The correlation coefficient R 2 of the model is 0.922, and the internal and external validation coefficient, Q 2 LOO and Q 2 ext , are 0.91 and 0.89 respectively, implying that the model has satisfactory goodness-of-fit, robustness, and predictive ability and thus provides a robust predictive tool to estimate the logK SiO/A values for chemicals in application domain. The applicability domain of the model was visualized by the Williams plot.

Using measured octanol-air partition coefficients to explain environmental partitioning of organochlorine pesticides.

PubMed

Shoeib, Mahiba; Harner, Tom

2002-05-01

Octanol-air partition coefficients (Koa) were measured directly for 19 organochlorine (OC) pesticides over the temperature range of 5 to 35 degrees C. Values of log Koa at 25 degrees C ranged over three orders of magnitude, from 7.4 for hexachlorobenzene to 10.1 for 1,1-dichloro-2,2-bis(p-chlorophenyl) ethane. Measured values were compared to values calculated as KowRT/H (where R is the ideal gas constant [8.314 J mol(-1) K(-1)], T is absolute temperature, and H is Henry's law constant) were, in general, larger. Discrepancies of up to three orders of magnitude were observed, highlighting the need for direct measurements of Koa. Plots of Koa versus inverse absolute temperature exhibited a log-linear correlation. Enthalpies of phase transition between octanol and air (deltaHoa) were determined from the temperature slopes and were in the range of 56 to 105 kJ mol(-1) K(-1). Activity coefficients in octanol (gamma(o)) were determined from Koa and reported supercooled liquid vapor pressures (pL(o)), and these were in the range of 0.3 to 12, indicating near-ideal solution behavior. Differences in Koa values for structural isomers of hexachlorocyclohexane were also explored. A Koa-based model was described for predicting the partitioning of OC pesticides to aerosols and used to calculate particulate fractions at 25 and -10 degrees C. The model also agreed well with experimental results for several OC pesticides that were equilibrated with urban aerosols in the laboratory. A log-log regression of the particle-gas partition coefficient versus Koa had a slope near unity, indicating that octanol is a good surrogate for the aerosol organic matter.

Partitioning of polycyclic aromatic hydrocarbons, alkylphenols, bisphenol A and phthalates in landfill leachates and stormwater.

PubMed

Kalmykova, Yuliya; Björklund, Karin; Strömvall, Ann-Margret; Blom, Lena

2013-03-01

Partitioning of organic pollutants is essential to their fate, mobility and removal from water and soil. To study the partitioning behavior of selected alkylphenols, bisphenol A, phthalates and polycyclic aromatic hydrocarbons (PAHs), a method for separating the truly dissolved and colloidal phase of organic pollutants was developed, verified and applied to samples of landfill leachate and stormwater from urban areas and waste-sorting sites. Alkylphenols, bisphenol A, phthalates and PAHs were detected in all the untreated samples (total concentrations), most of the filtered samples and frequently in the colloid-bound phase. Concentrations of alkylphenols and PAHs in urban stormwater were one order of magnitude lower than in the landfill leachates and stormwater from waste-sorting sites. The difference between total, dissolved and colloid-bound concentrations in the water samples was not statistically significant for any phenols or phthalates, but for three of the PAHs; naphthalene (mostly dissolved), phenanthrene and fluoranthene (mostly particulate). These results indicate that in landfill leachates and stormwaters, organic pollutants are predominantly attached to colloids and/or truly dissolved in contrast to their expected strong sorption to particulate matter. Occurrence and concentrations of pollutants in dissolved and colloid-bound phases correlated negatively with the K(OW). However, even highly hydrophobic compounds were frequently detected in filtered samples, i.e. the dissolved phases, and it is suggested that the organic content in the colloids decreases the compounds' partition to particles. The results confirm that the K(OW) values of specific organic pollutants well describe the compounds partition-binding process to dissolved organic carbon (DOC) colloids. Our findings call for a re-assessment of the organic pollutants' mobility and associated risks. This knowledge can also serve as a base for selecting efficient treatment methods for stormwater and landfill leachates. Copyright © 2012 Elsevier Ltd. All rights reserved.

Seasonal variation and partitioning of endocrine disrupting chemicals in waters and sediments of the Pearl River system, South China.

PubMed

Gong, Jian; Duan, Dandan; Yang, Yu; Ran, Yong; Chen, Diyun

2016-12-01

Endocrine disrupting chemicals (EDCs) were seasonally investigated in surface water, suspended particulate matter, and sediments of the Pearl River Delta (PRD), South China. EDC concentrations in the surface water were generally higher in the summer than in winter. The surface water in the investigated rivers was heavily contaminated by the phenolic xenoestrogens. Moreover, the in-situ log K soc and log K poc values and their regression with log K ow in the field experiments suggest that binding mechanisms other than hydrophobic interaction are present for the sedimentary organic carbon and particulate organic carbon (SOC/POC). The logK soc -logK ow and logK poc -logK ow regression analyses imply that higher complexity of nonhydrophobic interactions with EDCs is present on the SOC samples comparing with the POC samples, which is related to their different sources. Copyright © 2016 Elsevier Ltd. All rights reserved.

The Installation Restoration Program Toxicology Guide. Volume 3

DTIC Science & Technology

1989-07-01

zvli UW OF TABLES Volun.e 4 (Cont.) 69-3 Chemical Additives ............................ 69-15 69-4 Acute Toxicity of Components of Mineral Base...659. Values were estimated by Arthur D. little, Inc. uwing Kow as the basis of estimation (See Introduction, VoL 1). Values of less than one are very...Introduction, Vol. 1). 659. Values were etfiinated by Arthur D. little, In~c. uwing Kow as the basis of. estimation (See Introduction, Vol. 1). Values of

Effects of chronic alcohol consumption on dermal penetration of pesticides in rats.

PubMed

Brand, R M; Charron, A R; Dutton, L; Gavlik, T L; Mueller, C; Hamel, F G; Chakkalakal, D; Donohue, T M

2004-01-23

Topically applied ethanol is a well-known dermal penetration enhancer. The purpose of this work was to determine if ethanol consumption might also increase transdermal penetration. Male rats were fed either an ethanol containing or control diet for 6-8 wk. After the feeding regime was completed, skin was removed and placed in an in vitro diffusion system. The transdermal absorption of four very commonly used herbicides was determined. Penetration through skin from ethanol-fed rats was enhanced when compared to control by a factor of 5.3 for paraquat, 2.4 for atrazine, and 2.2 for 2,4-dichlorophenoxyacetic acid (2,4-D), and reduced by a factor 0.6 for trifluralin. Comparison of physical factors of the herbicides to the penetration enhancement revealed an inverse linear correlation with lipophilicity, as defined by log octanol/water partition coefficient (log Kow) with r2 =.98. These changes were at least partially reversible after 1 wk of abstinence from ethanol. These experiments demonstrate that regular ethanol consumption can alter the properties of the dermal barrier, leading to increased absorption of some chemicals through rat skin. If ethanol consumption has the same effect on human skin it could potentially have adverse health effects on people regularly exposed to agricultural, environmental, and industrial chemicals.

Bioaccumulation and trophic transfer of short chain chlorinated paraffins in a marine food web from Liaodong Bay, North China.

PubMed

Ma, Xindong; Zhang, Haijun; Wang, Zhen; Yao, Ziwei; Chen, Jingwen; Chen, Jiping

2014-05-20

Short chain chlorinated paraffins (SCCPs) are under the evaluation for inclusion into the Stockholm Convention on persistent organic pollutants. However, information on their bioconcentration and biomagnification in marine ecosystems is unavailable, limiting the evaluation of their ecological risks. In this study, seawater, sediment, zooplankton, invertebrates, and fishes collected from Liaodong Bay, Bohai Sea, North China were analyzed to investigate the residual level, congener group profile, bioaccumulation, and trophic transfer of SCCPs in a marine food web. The total concentrations of SCCPs ranged from 4.1 to 13.1 ng L(-1) in seawater, 65 to 541 ng g(-1) (dw) in sediment, and 86 to 4400 ng g(-1) (ww) in organisms. Correspondence analysis indicated the relative enrichment of C10Cl5 and C11Cl5 formula groups in most aquatic organisms. Both the logarithm bioaccumulation factors (log BAFs: 4.1-6.7) and biota-sediment accumulation factors (BSAFs: 0.1-7.3) of individual congeners implied the bioaccumulation of SCCPs. The trophic magnification factor (TMF) of ∑SCCPs was determined to be 2.38 in the zooplankton-shrimp-fish food web, indicating biomagnification potential of SCCPs in the marine ecosystem. The TMF values of individual congener groups significantly correlated with their log KOW values.

Precipitation scavenging of polychlorinated biphenyl congeners in the great lakes region

NASA Astrophysics Data System (ADS)

Murray, Michael W.; Andren, Anders W.

Ten precipitation events were sampled in the fall of 1986 in Madison, WI and analyzed for individual congener and total polychlorinated biphenyl (PCB) levels in both the dissolved and particulate phases. Total PCB concentrations were generally at the lower end of ranges recently reported for precipitation. Operationally defined dissolved and particulate phase congener distribution patterns for the two events of highest concentration were qualitatively similar to gas-phase and particle-bound patterns for northern Wisconsin air samples. Higher than predicted dissolved-phase concentrations may indicate non-equilibrium processes during scavenging and/or sample processing, the presence of colloids and micro-particulates, and/or more efficient gas-phase transfer to hydrometeors with organic coatings. Observed organic carbon-normalized distribution coefficients increased slightly with increasing octanol-water partition coefficient, giving the relationship log Koc = 0.22 log Kow + 4.64. The data indicate that a third organic-rich colloidal phase could be influencing partitioning, and could explain the higher than expected apparent gas scavenging efficiency for PCBs from the atmosphere. Precipitation-weighted mean fluxes of PCBs in the dissolved and particulate phases were 1.2 and 1.4 μg m -2 year -1, respectively, indicating that precipitation remains a significant source of PCBs to the upper Great Lakes.

Adsorption of Selected Pharmaceutical Compounds onto Activated Carbon in Dilute Aqueous Solutions Exemplified by Acetaminophen, Diclofenac, and Sulfamethoxazole.

PubMed

Chang, E-E; Wan, Jan-Chi; Kim, Hyunook; Liang, Chung-Huei; Dai, Yung-Dun; Chiang, Pen-Chi

2015-01-01

The adsorption of three pharmaceuticals, namely, acetaminophen, diclofenac, and sulfamethoxazole onto granular activated carbon (GAC), was investigated. To study competitive adsorption, both dynamic and steady-state adsorption experiments were conducted by careful selection of pharmaceuticals with various affinities and molecular size. The effective diffusion coefficient of the adsorbate was increased with decease in particle size of GAC. The adsorption affinity represented as Langmuir was consistent with the ranking of the octanol-water partition coefficient, K(ow). The adsorption behavior in binary or tertiary systems could be described by competition adsorption. In the binary system adsorption replacement occurred, under which the adsorbate with the smaller K(ow) was replaced by the one with larger K(ow). Results also indicated that portion of the micropores could be occupied only by the small target compound, but not the larger adsorbates. In multiple-component systems the competition adsorption might significantly be affected by the macropores and less by the meso- or micropores.

Application of ultrasound and quartz sand for the removal of disinfection byproducts from drinking water.

PubMed

Yang, Wu; Dong, Lili; Luo, Zhen; Cui, Xiaochun; Liu, Jiancong; Liu, Zhongmou; Huo, Mingxin

2014-04-01

To the best of our knowledge, little information is available on the combined use of ultrasound (US) and quartz sand (QS) in the removal of disinfection byproducts (DBPs) from drinking water. This study investigates the removal efficiency for 12 DBPs from drinking water by 20 kHz sonolytic treatment, QS adsorption, and their combination. Results indicate that DBPs with logKow≤1.12 could not be sonolysized; for logKow≥1.97, more than 20% removal efficiency was observed, but the removal efficiency was unrelated to logKow. DBPs containing a nitro group are more sensitive to US than those that comprise nitrile, hydrogen, and hydroxyl groups. Among the 12 investigated DBPs, 9 could be adsorbed by QS adsorption. The adsorption efficiency ranged from 12% for 1,1-dichloro-2-propanone to 80% for trichloroacetonitrile. A synergistic effect was found between the US and QS on DBPs removal, and all the 12 DBPs could be effectively removed by the combined use of US and QS. In the presence of US, part of the QS particles were corroded into small particles which play a role in increasing the number of cavitation bubbles and reducing cavitation bubble size and then improve the removal efficiency of DBPs. On the other hand, the presence of US enhances the DBP mass transfer rate to cavitation bubbles and quartz sand. In addition, sonolytic treatment led to a slight decrease of pH, and TOC values decreased under all the three treatment processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

Physicochemical properties of selected polybrominated diphenyl ethers and extension of the UNIFAC model to brominated aromatic compounds.

PubMed

Kuramochi, Hidetoshi; Maeda, Kouji; Kawamoto, Katsuya

2007-04-01

The aqueous solubilities (S(w)) at various temperatures from 283 K to 308 K and 1-octanol/water partition coefficients (K(ow)) for four polybrominated diphenyl ethers (PBDEs: 4,4'-dibromodiphenyl ether (BDE-15), 2,2',4,4'-tetrabromodiphenyl ether (BDE-47), 2,2',4,4',5-pentabromodiphenyl ether (BDE-99), and 2,2',4,4',5,5'-hexabromodiphenyl ether (BDE-153)) were measured by the generator column method. The S(w) and K(ow) data revealed the effect of bromine substitution and basic structure on S(w) and K(ow). To estimate the infinite dilution activity coefficients (gamma(i)(w,infinity)) of the PBDEs in water from the S(w) data, enthalpies of fusion and melting points for those compounds were measured with a differential scanning calorimeter. Henry's Law constants (H(w)) of the PBDEs were derived from the determined gamma(i)(w,infinity) and literature vapor pressure data. Some physicochemical characteristics of PBDEs were also suggested by comparing the present property data with that of polychlorinated dibenzo-p-dioxins, brominated phenols and brominated benzenes in past studies. Furthermore, in order to represent different phase equilibria including solubility and partition equilibrium for other brominated aromatic compounds using the UNIFAC model, a pair of UNIFAC group interaction parameters between the bromine and water group were determined from the S(w) and K(ow) data of PBDEs and brominated benzenes. The ability of the determined parameters to represent both properties of brominated aromatics was evaluated.

Flash Nanoprecipitation: Prediction and Enhancement of Particle Stability via Drug Structure

PubMed Central

2015-01-01

Flash nanoprecipitation (FNP) can generate hydrophobic drug nanoparticles in ∼100 nm with a much higher drug loading (e.g., > 40 wt %) than traditional nanocarriers (e.g., < 20 wt %). This paper studies the effects of drug molecules on nanoparticle stability made via FNP and demonstrates that chemically bonding a drug compound (e.g., paclitaxel) with a cleavable hydrophobic moiety of organosilicate (e.g., triethoxysilicate) is able to enhance the particle size stability. A nonionic amphiphilic diblock copolymer, poly(lactic-co-glycolic acid)-block-poly(ethylene glycol) (PLGA-b-PEG), is used as a model surfactant to provide steric stabilization. The experiments here show that the lower the drug solubility in the aqueous medium, the more stable the particles in terms of Ostwald ripening, which are consistent with the prediction by the LSW theory. The initial particle size distribution is sufficiently narrow and of insignificance to Ostwald ripening. To correlate the particle stability with hydrophobicity, this study introduces the n-octanol/water partition coefficient (LogP), a hydrophobicity indication, into the FNP technique. A comparison of various drugs and their analogues shows that LogP of a drug is a better hydrophobicity indication than the solubility parameter (δ) and correlates well with the particle stability. Empirically, with ACDLogP > ∼12, nanoparticles have good stability; with ∼2 < ACDLogP < ∼9, nanoparticles show fast Ostwald ripening and interparticle recrystallization; with ACDLogP < ∼2, the drug is very likely difficult to form nanoparticles. This rule creates a quick way to predict particle stability for a randomly selected drug structure and helps to enable a fast preclinical drug screen. PMID:24484077

Estimation of uptake rate constants for PCB congeners accumulated by semipermeable membrane devices and brown treat (Salmo trutta)

USGS Publications Warehouse

Meadows, J.C.; Echols, K.R.; Huckins, J.N.; Borsuk, F.A.; Carline, R.F.; Tillitt, D.E.

1998-01-01

The triolein-filled semipermeable membrane device (SPMD) is a simple and effective method of assessing the presence of waterborne hydrophobic chemicals. Uptake rate constants for individual chemicals are needed to accurately relate the amounts of chemicals accumulated by the SPMD to dissolved water concentrations. Brown trout and SPMDs were exposed to PCB- contaminated groundwater in a spring for 28 days to calculate and compare uptake rates of specific PCB congeners by the two matrixes. Total PCB congener concentrations in water samples from the spring were assessed and corrected for estimated total organic carbon (TOC) sorption to estimate total dissolved concentrations. Whole and dissolved concentrations averaged 4.9 and 3.7 ??g/L, respectively, during the exposure. Total concentrations of PCBs in fish rose from 0.06 to 118.3 ??g/g during the 28-day exposure, while concentrations in the SPMD rose from 0.03 to 203.4 ??g/ g. Uptake rate constants (k1) estimated for SPMDs and brown trout were very similar, with k1 values for SPMDs ranging from one to two times those of the fish. The pattern of congener uptake by the fish and SPMDs was also similar. The rates of uptake generally increased or decreased with increasing K(ow), depending on the assumption of presence or absence of TOC.The triolein-filled semipermeable membrane device (SPMD) is a simple and effective method of assessing the presence of waterborne hydrophobic chemicals. Uptake rate constants for individual chemicals are needed to accurately relate the amounts of chemicals accumulated by the SPMB to dissolved water concentrations. Brown trout and SPMDs were exposed to PCB-contaminated groundwater in a spring for 28 days to calculate and compare uptake rates of specific PCB congeners by the two matrixes. Total PCB congener concentrations in water samples from the spring were assessed and corrected for estimated total organic carbon (TOC) sorption to estimate total dissolved concentrations. Whole and dissolved concentrations averaged 4.9 and 3.7 ??g/L, respectively, during the exposure. Total concentrations of PCBs in fish rose from 0.06 to 118.3 ??g/g during the 28-day exposure, while concentrations in the SPMD rose from 0.03 to 203.4 ??g/g. Uptake rate constants (k1) estimated for SPMDs and brown trout were very similar, with k1 values for SPMDs ranging from one to two times those of the fish. The pattern of congener uptake by the fish and SPMBs was also similar. The rates of uptake generally increased or decreased with increasing KOW, depending on the assumption of presence or absence of TOC.

Improvements in pollutant monitoring: optimizing silicone for co-deployment with polyethylene passive sampling devices.

PubMed

O'Connell, Steven G; McCartney, Melissa A; Paulik, L Blair; Allan, Sarah E; Tidwell, Lane G; Wilson, Glenn; Anderson, Kim A

2014-10-01

Sequestering semi-polar compounds can be difficult with low-density polyethylene (LDPE), but those pollutants may be more efficiently absorbed using silicone. In this work, optimized methods for cleaning, infusing reference standards, and polymer extraction are reported along with field comparisons of several silicone materials for polycyclic aromatic hydrocarbons (PAHs) and pesticides. In a final field demonstration, the most optimal silicone material is coupled with LDPE in a large-scale study to examine PAHs in addition to oxygenated-PAHs (OPAHs) at a Superfund site. OPAHs exemplify a sensitive range of chemical properties to compare polymers (log Kow 0.2-5.3), and transformation products of commonly studied parent PAHs. On average, while polymer concentrations differed nearly 7-fold, water-calculated values were more similar (about 3.5-fold or less) for both PAHs (17) and OPAHs (7). Individual water concentrations of OPAHs differed dramatically between silicone and LDPE, highlighting the advantages of choosing appropriate polymers and optimized methods for pollutant monitoring. Copyright © 2014 Elsevier Ltd. All rights reserved.

IMPROVEMENTS IN POLLUTANT MONITORING: OPTIMIZING SILICONE FOR CO-DEPLOYMENT WITH POLYETHYLENE PASSIVE SAMPLING DEVICES

PubMed Central

O’Connell, Steven G.; McCartney, Melissa A.; Paulik, L. Blair; Allan, Sarah E.; Tidwell, Lane G.; Wilson, Glenn; Anderson, Kim A.

2014-01-01

Sequestering semi-polar compounds can be difficult with low-density polyethylene (LDPE), but those pollutants may be more efficiently absorbed using silicone. In this work, optimized methods for cleaning, infusing reference standards, and polymer extraction are reported along with field comparisons of several silicone materials for polycyclic aromatic hydrocarbons (PAHs) and pesticides. In a final field demonstration, the most optimal silicone material is coupled with LDPE in a large-scale study to examine PAHs in addition to oxygenated-PAHs (OPAHs) at a Superfund site. OPAHs exemplify a sensitive range of chemical properties to compare polymers (log Kow 0.2–5.3), and transformation products of commonly studied parent PAHs. On average, while polymer concentrations differed nearly 7-fold, water-calculated values were more similar (about 3.5-fold or less) for both PAHs (17) and OPAHs (7). Individual water concentrations of OPAHs differed dramatically between silicone and LDPE, highlighting the advantages of choosing appropriate polymers and optimized methods for pollutant monitoring. PMID:25009960

Bioconcentration factors and lipid solubility

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

Banerjee, S.; Baughman, G.L.

1991-03-01

The log-log relationship between bioconcentration and hydrophobicity breaks down for several medium and high molecular weight solutes that bioconcentrate either to a small extent or not at all. Much of the failure is attributed to the relatively low solubility of these compounds in lipid. Inclusion of a term in octanol solubility (in place of lipid solubility, which is generally unavailable) considerably improves the quality of the relationship (r = 0.95). It is speculated that the octanol solubility term compensates for the relatively low solubility of large compounds in lipid.

Electrochemical Genotoxicity Assay Based on a SOS/umu Test Using Hydrodynamic Voltammetry in a Droplet

PubMed Central

Kuramitz, Hideki; Sazawa, Kazuto; Nanayama, Yasuaki; Hata, Noriko; Taguchi, Shigeru; Sugawara, Kazuharu; Fukushima, Masami

2012-01-01

The SOS/umu genotoxicity assay evaluates the primary DNA damage caused by chemicals from the β-galactosidase activity of S. typhimurium. One of the weaknesses of the common umu test system based on spectrophotometric detection is that it is unable to measure samples containing a high concentration of colored dissolved organic matters, sediment, and suspended solids. However, umu tests with electrochemical detection techniques prove to be a better strategy because it causes less interference, enables the analysis of turbid samples and allows detection even in small volumes without loss of sensitivity. Based on this understanding, we aim to develop a new umu test system with hydrodynamic chronoamperometry using a rotating disk electrode (RDE) in a microliter droplet. PAPG when used as a substrate is not electroactive at the potential at which PAP is oxidized to p-quinone imine (PQI), so the current response of chronoamperometry resulting from the oxidation of PAP to PQI is directly proportional to the enzymatic activity of S. typhimurium. This was achieved by performing genotoxicity tests for 2-(2-furyl)-3-(5-nitro-2-furyl)-acrylamide (AF-2) and 2-aminoanthracene (2-AA) as model genotoxic compounds. The results obtained in this study indicated that the signal detection in the genotoxicity assay based on hydrodynamic voltammetry was less influenced by the presence of colored components and sediment particles in the samples when compared to the usual colorimetric signal detection. The influence caused by the presence of humic acids (HAs) and artificial sediment on the genotoxic property of selected model compounds such as 4-nitroquinoline-N-oxide (4-NQO), 3-chloro-4-(dichloromethyl)-5-hydroxy-2(5H)-furanone (MX), 1,8-dinitropyrene (1,8-DNP) and 1-nitropyrene (1-NP) were also investigated. The results showed that the genotoxicity of 1-NP and MX changed in the presence of 10 mg·L−1 HAs. The genotoxicity of tested chemicals with a high hydrophobicity such as 1,8-DNP and 1-NP were decreased substantially with the presence of 1 g·L−1 sediment. This was not observed in the case of genotoxins with a low log Kow value. PMID:23242275

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.

Octanol-water partition coefficients for predicting the effects of tannins in ruminant nutrition.

PubMed

Mueller-Harvey, Irene; Mlambo, Victor; Sikosana, Joe L N; Smith, Tim; Owen, Emyr; Brown, Ron H

2007-07-11

Tannins can cause beneficial or harmful nutritional effects, but their great diversity has until now prevented a rational distinction between tannin structures and their nutritional responses. An attempt has been made to study this problem by examining the octanol-water solubilities of tannins. A relatively simple HPLC method has been developed for screening mixtures of plant tannins for their octanol-water partition coefficients (Kow coefficients). Tannins were isolated from the fruits and leaves of different Acacia, Calliandra, Dichrostachys, and Piliostigma species, which are known to produce beneficial or harmful effects. The Kow coefficients of these tannins ranged from 0.061 to 13.9, average coefficients of variation were 9.2% and recoveries were 107%. Acacia nilotica fruits and leaves had the highest Kow coefficients, that is, 2.0 and 13.9, respectively. These A. nilotica products also have high concentrations of tannins. The combined effects of high octanol solubilities and high tannin concentrations may explain their negative effects on animal nutrition and health. It is known that compounds with high octanol solubilities are more easily absorbed into tissues, and it is, therefore, proposed that such compounds are more likely to cause toxicity problems especially if consumed in large quantities. According to the literature, tannins in human foods tend to have low Kow coefficients, and this was confirmed for the tannins in Piliostigma thonningii fruits. Therefore, unconventional feeds or browse products should be screened not only for their tannin concentrations but also for low octanol-water partition coefficients in order to identify nutritionally safe feeds and to avoid potentially toxic feeds.

Insight into the adsorption of PPCPs by porous adsorbents: Effect of the properties of adsorbents and adsorbates.

PubMed

Zhu, Zengyin; Xie, Jiawen; Zhang, Mancheng; Zhou, Qing; Liu, Fuqiang

2016-07-01

Adsorption is an efficient method for removal of pharmaceuticals and personal care products (PPCPs). Magnetic resins are efficient adsorbents for water treatment and exhibit potential for PPCP removal. In this study, the magnetic hypercrosslinked resin Q100 was used for adsorption of PPCPs. The adsorption behavior of this resin was compared with those of two activated carbons, namely, Norit and F400D. Norit exhibited the fastest adsorption kinetics, followed by Q100. Norit featured a honeycomb shape and long-range ordered pore channels, which facilitated the diffusion of PPCPs. Moreover, the large average pore size of Q100 reduced diffusion resistance. The adsorbed amounts of 11 PPCPs on the three adsorbents increased with increasing adsorbate hydrophobicity. For Q100, a significant linear correlation was observed between the adsorption performance for PPCPs and hydrophobicity (logD value) of adsorbates (R(2) = 0.8951); as such, PPCPs with high logD values (>1.69) could be efficiently removed. Compared with those of Norit and F400D, the adsorption performance of Q100 was less affected by humic acid because of the dominant hydrophobic interaction. Furthermore, Q100 showed improved regeneration performance, which renders it promising for PPCP removal in practical applications. Copyright © 2016 Elsevier Ltd. All rights reserved.

Why Amphibians Are More Sensitive than Mammals to Xenobiotics

PubMed Central

Quaranta, Angelo; Bellantuono, Vito; Cassano, Giuseppe; Lippe, Claudio

2009-01-01

Dramatic declines in amphibian populations have been described all over the world since the 1980s. The evidence that the sensitivity to environmental threats is greater in amphibians than in mammals has been generally linked to the observation that amphibians are characterized by a rather permeable skin. Nevertheless, a numerical comparison of data of percutaneous (through the skin) passage between amphibians and mammals is lacking. Therefore, in this investigation we have measured the percutaneous passage of two test molecules (mannitol and antipyrine) and three heavily used herbicides (atrazine, paraquat and glyphosate) in the skin of the frog Rana esculenta (amphibians) and of the pig ear (mammals), by using the same experimental protocol and a simple apparatus which minimizes the edge effect, occurring when the tissue is clamped in the usually used experimental device. The percutaneous passage (P) of each substance is much greater in frog than in pig. LogP is linearly related to logKow (logarithm of the octanol-water partition coefficient). The measured P value of atrazine was about 134 times larger than that of glyphosate in frog skin, but only 12 times in pig ear skin. The FoD value (Pfrog/Ppig) was 302 for atrazine, 120 for antipyrine, 66 for mannitol, 29 for paraquat, and 26 for glyphosate. The differences in structure and composition of the skin between amphibians and mammals are discussed. PMID:19888346

Why amphibians are more sensitive than mammals to xenobiotics.

PubMed

Quaranta, Angelo; Bellantuono, Vito; Cassano, Giuseppe; Lippe, Claudio

2009-11-04

Dramatic declines in amphibian populations have been described all over the world since the 1980s. The evidence that the sensitivity to environmental threats is greater in amphibians than in mammals has been generally linked to the observation that amphibians are characterized by a rather permeable skin. Nevertheless, a numerical comparison of data of percutaneous (through the skin) passage between amphibians and mammals is lacking. Therefore, in this investigation we have measured the percutaneous passage of two test molecules (mannitol and antipyrine) and three heavily used herbicides (atrazine, paraquat and glyphosate) in the skin of the frog Rana esculenta (amphibians) and of the pig ear (mammals), by using the same experimental protocol and a simple apparatus which minimizes the edge effect, occurring when the tissue is clamped in the usually used experimental device.The percutaneous passage (P) of each substance is much greater in frog than in pig. LogP is linearly related to logKow (logarithm of the octanol-water partition coefficient). The measured P value of atrazine was about 134 times larger than that of glyphosate in frog skin, but only 12 times in pig ear skin. The FoD value (Pfrog/Ppig) was 302 for atrazine, 120 for antipyrine, 66 for mannitol, 29 for paraquat, and 26 for glyphosate.The differences in structure and composition of the skin between amphibians and mammals are discussed.

Effect of cell-surface hydrophobicity on bacterial conversion of water-immiscible chemicals in two-liquid-phase culture systems.

PubMed

Hamada, Takahiro; Maeda, Yusuke; Matsuda, Hiroyuki; Sameshima, Yuka; Honda, Kohsuke; Omasa, Takeshi; Kato, Junichi; Ohtake, Hisao

2009-08-01

The effect of bacterial cell-surface hydrophobicity on the bioconversion of water-immiscible chemicals in an aqueous-organic (A/O) two-liquid-phase culture system was investigated. Escherichia coli JM109 and Rhodococcus opacus B-4 were used as hydrophilic and hydrophobic whole-cell catalysts, respectively. Hydroxylation reactions of monoaromatics, including toluene (log P(ow)=2.9), ethylbenzene (3.1), n-propylbenzene (3.4), and sec-butylbenzene (3.7), were employed as model conversions. When the todC1C2BA genes encoding Pseudomonas putida toluene dioxygenase were expressed in E. coli JM109, the yield of hydroxylated monoaromatics decreased with increasing substrate hydrophobicity. By contrast, R. opacus transformants, which expressed the todC1C2BA genes, showed high performance in the hydroxylation of monoaromatics, irrespective of substrate hydrophobicity. When the R. opacus transformants were examined for their ability to hydroxylate monoaromatics in an aqueous single-liquid-phase culture, the reaction velocity was markedly lower than that observed in the A/O two-liquid-phase culture. These results suggested that R. opacus B-4 accessed the hydrophobic substrates in the oil phase, thus making it more effective for the bioconversion reactions.

In vitro to in vivo extrapolation of biotransformation rates for assessing bioaccumulation of hydrophobic organic chemicals in mammals.

PubMed

Lee, Yung-Shan; Lo, Justin C; Otton, S Victoria; Moore, Margo M; Kennedy, Chris J; Gobas, Frank A P C

2017-07-01

Incorporating biotransformation in bioaccumulation assessments of hydrophobic chemicals in both aquatic and terrestrial organisms in a simple, rapid, and cost-effective manner is urgently needed to improve bioaccumulation assessments of potentially bioaccumulative substances. One approach to estimate whole-animal biotransformation rate constants is to combine in vitro measurements of hepatic biotransformation kinetics with in vitro to in vivo extrapolation (IVIVE) and bioaccumulation modeling. An established IVIVE modeling approach exists for pharmaceuticals (referred to in the present study as IVIVE-Ph) and has recently been adapted for chemical bioaccumulation assessments in fish. The present study proposes and tests an alternative IVIVE-B technique to support bioaccumulation assessment of hydrophobic chemicals with a log octanol-water partition coefficient (K OW ) ≥ 4 in mammals. The IVIVE-B approach requires fewer physiological and physiochemical parameters than the IVIVE-Ph approach and does not involve interconversions between clearance and rate constants in the extrapolation. Using in vitro depletion rates, the results show that the IVIVE-B and IVIVE-Ph models yield similar estimates of rat whole-organism biotransformation rate constants for hypothetical chemicals with log K OW  ≥ 4. The IVIVE-B approach generated in vivo biotransformation rate constants and biomagnification factors (BMFs) for benzo[a]pyrene that are within the range of empirical observations. The proposed IVIVE-B technique may be a useful tool for assessing BMFs of hydrophobic organic chemicals in mammals. Environ Toxicol Chem 2017;36:1934-1946. © 2016 SETAC. © 2016 SETAC.

In silico modelling of drug–polymer interactions for pharmaceutical formulations

PubMed Central

Ahmad, Samina; Johnston, Blair F.; Mackay, Simon P.; Schatzlein, Andreas G.; Gellert, Paul; Sengupta, Durba; Uchegbu, Ijeoma F.

2010-01-01

Selecting polymers for drug encapsulation in pharmaceutical formulations is usually made after extensive trial and error experiments. To speed up excipient choice procedures, we have explored coarse-grained computer simulations (dissipative particle dynamics (DPD) and coarse-grained molecular dynamics using the MARTINI force field) of polymer–drug interactions to study the encapsulation of prednisolone (log p = 1.6), paracetamol (log p = 0.3) and isoniazid (log p = −1.1) in poly(l-lactic acid) (PLA) controlled release microspheres, as well as the encapsulation of propofol (log p = 4.1) in bioavailability enhancing quaternary ammonium palmitoyl glycol chitosan (GCPQ) micelles. Simulations have been compared with experimental data. DPD simulations, in good correlation with experimental data, correctly revealed that hydrophobic drugs (prednisolone and paracetamol) could be encapsulated within PLA microspheres and predicted the experimentally observed paracetamol encapsulation levels (5–8% of the initial drug level) in 50 mg ml−1 PLA microspheres, but only when initial paracetamol levels exceeded 5 mg ml−1. However, the mesoscale technique was unable to model the hydrophilic drug (isoniazid) encapsulation (4–9% of the initial drug level) which was observed in experiments. Molecular dynamics simulations using the MARTINI force field indicated that the self-assembly of GCPQ is rapid, with propofol residing at the interface between micellar hydrophobic and hydrophilic groups, and that there is a heterogeneous distribution of propofol within the GCPQ micelle population. GCPQ–propofol experiments also revealed a population of relatively empty and drug-filled GCPQ particles. PMID:20519214

Bioconcentration of lipophilic compounds by some aquatic organisms

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

Hawker, D.W.; Connell, D.W.

1986-04-01

With nondegradable, lipophilic compounds having log P values ranging from 2 to 6, direct linear relationships have been found between the logarithms of the equilibrium bioconcentration factors, and also reciprocal clearance rate constants, with log P for daphnids and molluscs. These relationships permit calculation of the times required for equilibrium and significant bioconcentration of lipophilic chemicals. Compared with fish, these time periods are successively shorter for molluscs, then daphnids. The equilibrium biotic concentration was found to decrease with increasing chemical hydrophobicity for both molluscs and daphnids. Also, new linear relationships between the logarithm of the bioconcentration factor and log Pmore » were found for compounds not attaining equilibrium within finite exposure times.« less

Ag/C:F Antibacterial and hydrophobic nanocomposite coatings

NASA Astrophysics Data System (ADS)

Kylián, Ondřej; Kratochvíl, Jiří; Petr, Martin; Kuzminova, Anna; Slavínská, Danka; Biederman, Hynek; Beranová, Jana

Silver-based nanomaterials that exhibit antibacterial character are intensively studied as they represent promising weapon against multi-drug resistant bacteria. Equally important class of materials represent coatings that have highly water repellent nature. Such materials may be used for fabrication of anti-fogging or self-cleaning surfaces. The aim of this study is to combine both of these valuable material characteristics. Antibacterial and highly hydrophobic Ag/C:F nanocomposite films were fabricated by means of gas aggregation source of Ag nanoparticles and sputter deposition of C:F matrix. The nanocomposite coatings had three-layer structure C:F base layer/Ag nanoparticles/C:F top layer. It is shown that the increasing number of Ag nanoparticles in produced coatings leads not only in enhancement of their antibacterial activity, but also causes substantial increase of their hydrophobicity. Under optimized conditions, the coatings are super-hydrophobic with water contact angle equal to 165∘ and are capable to induce 6-log reduction of bacteria presented in solution within 4h.

Adsorption of selected endocrine disrupting compounds and pharmaceuticals on activated biochars.

PubMed

Jung, Chanil; Park, Junyeong; Lim, Kwang Hun; Park, Sunkyu; Heo, Jiyong; Her, Namguk; Oh, Jeill; Yun, Soyoung; Yoon, Yeomin

2013-12-15

Chemically activated biochar produced under oxygenated (O-biochar) and oxygen-free (N-biochar) conditions were characterized and the adsorption of endocrine disrupting compounds (EDCs): bisphenol A (BPA), atrazine (ATR), 17 α-ethinylestradiol (EE2), and pharmaceutical active compounds (PhACs); sulfamethoxazole (SMX), carbamazepine (CBM), diclofenac (DCF), ibuprofen (IBP) on both biochars and commercialized powdered activated carbon (PAC) were investigated. Characteristic analysis of adsorbents by solid-state nuclear magnetic resonance (NMR) was conducted to determine better understanding about the EDCs/PhACs adsorption. N-biochar consisted of higher polarity moieties with more alkyl (0-45 ppm), methoxyl (45-63 ppm), O-alkyl (63-108 ppm), and carboxyl carbon (165-187 ppm) content than other adsorbents, while aromaticity of O-biochar was higher than that of N-biochar. O-biochar was composed mostly of aromatic moieties, with low H/C and O/C ratios compared to the highly polarized N-biochar that contained diverse polar functional groups. The higher surface area and pore volume of N-biochar resulted in higher adsorption capacity toward EDCs/PhACs along with atomic-level molecular structural property than O-biochar and PAC. N-biochar had a highest adsorption capacity of all chemicals, suggesting that N-biochar derived from loblolly pine chip is a promising sorbent for agricultural and environmental applications. The adsorption of pH-sensitive dissociable SMX, DCF, IBP, and BPA varied and the order of adsorption capacity was correlated with the hydrophobicity (Kow) of adsorbates throughout the all adsorbents, whereas adsorption of non-ionizable CBM, ATR, and EE2 in varied pH allowed adsorbents to interact with hydrophobic property of adsorbates steadily throughout the study. Copyright © 2013 Elsevier B.V. All rights reserved.

Variation in net trophic transfer efficiencies among 21 PCB congeners

USGS Publications Warehouse

Madenjian, C.P.; Schmidt, L.J.; Chernyak, S.M.; Elliott, R.F.; Desorcie, T.J.; Quintal, R.T.; Begnoche, L.J.; Hesselberg, R.J.

1999-01-01

We tested the hypothesis that the efficiency with which fish retain polychlorinated biphenyl (PCB) congeners from their food strongly depends on Kow and degree of chlorination of the congener. We used diet information, determinations of concentrations of individual PCB congeners in both coho salmon (Oncorhynchus kisutch) and their prey, and bioenergetics modeling to estimate the efficiencies with which Lake Michigan coho salmon retain various PCB congeners from their food. The retention efficiency for the tetrachloro congeners averaged 38%, whereas retention efficiencies for higher chlorinated congeners ranged from 43 to 56%. Not including tetrachloro congeners, we found neither decreasing nor increasing trends in the efficiencies with which the coho salmon retained the PCB congeners from their food with either increasing Kow or increasing degree of chlorination of the PCB congeners. We concluded that (a) for PCB congeners with 5−8 chlorine atoms/molecule, Kow and degree of chlorination had little influence on the efficiency with which coho salmon retained the various PCB congeners in their food, and (b) the efficiency with which coho salmon retained tetrachloro PCB congeners in their food appeared to be slightly lower than that for higher chlorinated PCB congeners.

Cytotoxicity of alkylphenols and alkylated non-phenolics in a primary culture of rainbow trout (Onchorhynchus mykiss) hepatocytes.

PubMed

Tollefsen, K-E; Blikstad, Camilla; Eikvar, Sissel; Farmen Finne, Eivind; Katharina Gregersen, Inger

2008-01-01

Alkylphenols are common aquatic pollutants originating from industrial use of the compounds themselves or as biodegradation products of alkylphenol polyethoxylates. The cytotoxicity of a range of alkylphenols and alkylated non-phenolics were assessed in a primary culture of rainbow trout (Onchorhynchus mykiss) hepatocytes to construct a structure-toxicity relationship for this group of ubiquitous aquatic pollutants. Metabolic inhibition and loss of membrane integrity were used as cytotoxic endpoints through use of the cellular markers Alamar blue and 5-carboxyfluorescein diacetate acetoxymethyl ester, respectively. The results show that cytotoxicity increased with the hydrophobicity of the alkylphenols for compounds with logK(OW)<4.9. Normal chained alkylphenols, branched alkylphenols and multi-substituted alkylphenols with logK(OW)4.9 deviated clearly from this relationship. The alkylphenols displayed greater cytotoxicity than alkylated non-phenolics and it is proposed that most alkylated non-phenolic caused non-polar narcosis (baseline toxicity) whereas the alkylphenols caused polar narcosis. Observations that metabolic inhibition occurred at lower concentrations than loss of membrane integrity for most chemicals indicated that interference with cellular metabolic functions was the main cause of cytotoxicity. Metabolic inhibition corresponded better than loss of membrane integrity to reported acute toxicity to fish, although the in vivo acute toxicity of hydrophobic compounds (logK(OW)>2-3) was clearly underestimated by both endpoints.

Tissue distribution of co-planar and non-planar tetra- and hexa-chlorobiphenyl isomers in guinea pigs after oral ingestion

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

Jan, J.; Logar, B.; Jan, J.

1996-03-01

Food ingestion is the most important route for the uptake of lipophilic organochlorine contaminants. Uptake and transfer of the contaminants from the digestive tract to target organs can be used for risk evaluation. The bioconcentration and migration of polychlorobiphenyls (PCBs) is highly structure - dependent. Bioconcentration is correlated with lipophilicity on the basis of the n-octanol/water partition coefficient in its logarithmic form - logKow. However, some factors e.g. diffusion through cell membranes, accumulation in specific organs and tissues, uptake and deputation kinetics and metabolism can also influence the bioconcentration. Individual PCB compounds of commercial PCB preparation are taken up bymore » organisms to markedly different extents. Until now little is known about the distribution of non-planar and co-planar PCBs in different tissues. Co-planar PCBs have dioxin - like toxicity. This study examines differences in the bioconcentration of two pairs of tetra and hexa chlorobiphenyls from the digestive tract and their distribution in different tissues of guinea pigs.« less

Fate of higher brominated PBDEs in lactating cows.

PubMed

Kierkegaard, Amelie; Asplund, Lillemor; de Wit, Cynthia A; McLachlan, Michael S; Thomas, Gareth O; Sweetman, Andrew J; Jones, Kevin C

2007-01-15

Dietary intake studies of lower brominated diphenyl ethers (BDEs) have shown that fish and animal products are important vectors of human exposure, but almost no data exist for higher brominated BDEs. Therefore, the fate of hepta- to decaBDEs was studied in lactating cows exposed to a naturally contaminated diet by analyzing feed, feces, and milk samples from a previous mass balance study of PCB. Tissue distribution was studied in one cow slaughtered after the experiment. BDE-209 was the dominant congener in feed, organs, adipose tissues, and feces, but not in milk. In contrast to PCBs and lower brominated BDEs, concentrations of hepta- to decaBDEs in adipose tissue were 9-80 times higher than in milk fat and the difference increased with degree of bromination/log K(OW). The congener profiles in adipose tissue and feed differed; BDE-207, BDE-196, BDE-197, and BDE-182 accumulated to a surprisingly greater extent in the fat compared to their isomers, suggesting metabolic debromination of BDE-209 to these BDEs. The results indicate that meat rather than dairy product consumption may be an important human exposure route to higher brominated BDEs.

Evaluation of transfer rates of multiple pesticides from green tea into infusion using water as pressurized liquid extraction solvent and ultra-performance liquid chromatography tandem mass spectrometry.

PubMed

Chen, Hongping; Pan, Meiling; Liu, Xin; Lu, Chengyin

2017-02-01

Pesticide residues could be transferred from tea into its infusion and by-products, and subsequently consumed by humans. Extra extraction conditions may induce more pesticide leaching into the infusion and by-products of tea and cause greater damage to humans. The aim of this study is to evaluate the infusion of multiple pesticides from green tea into hot water via pressurized liquid extraction. The results showed that pesticides in spiked samples generally have higher leaching (0.8-45.0%) than those in the positive samples. There was a marked rise of transfer rates when water solubility increased from 20mgL(-1) to 450mgL(-1) and LogKow decreased from 6 to 4. All pesticides had more leaching into hot water using pressurized liquid extraction than traditional tea brewing. This study helps in risk assessment of pesticide residues and in the formulation of maximum residue levels (MRLs) in tea and its by-products. Copyright © 2016 Elsevier Ltd. All rights reserved.

A linear solvation energy relationship model of organic chemical partitioning to dissolved organic carbon.

PubMed

Kipka, Undine; Di Toro, Dominic M

2011-09-01

Predicting the association of contaminants with both particulate and dissolved organic matter is critical in determining the fate and bioavailability of chemicals in environmental risk assessment. To date, the association of a contaminant to particulate organic matter is considered in many multimedia transport models, but the effect of dissolved organic matter is typically ignored due to a lack of either reliable models or experimental data. The partition coefficient to dissolved organic carbon (K(DOC)) may be used to estimate the fraction of a contaminant that is associated with dissolved organic matter. Models relating K(DOC) to the octanol-water partition coefficient (K(OW)) have not been successful for many types of dissolved organic carbon in the environment. Instead, linear solvation energy relationships are proposed to model the association of chemicals with dissolved organic matter. However, more chemically diverse K(DOC) data are needed to produce a more robust model. For humic acid dissolved organic carbon, the linear solvation energy relationship predicts log K(DOC) with a root mean square error of 0.43. Copyright © 2011 SETAC.

Net trophic transfer efficiencies of polychlorinated biphenyl congeners to lake whitefish (Coregonus clupeaformis) from their food

USGS Publications Warehouse

Madenjian, C.P.; O'Connor, D.V.; Rediske, R.R.; O'Keefe, J. P.; Pothoven, S.A.

2008-01-01

Lake whitefish (Coregonus clupeaformis) were fed rainbow smelt (Osmerus mordax) in four laboratory tanks over a 133-d experiment. At the start of the experiment, 10 to 14 of the fish in each tank were sacrificed, and the concentrations of 40 polychlorinated biphenyl (PCB) congeners within these fish were determined. Polychlorinated biphenyl congener concentrations were also determined in the 15 lake whitefish remaining in each of the four tanks at the end of the experiment as well as in the rainbow smelt fed to the lake whitefish. Each lake whitefish was weighed at the start and the end of the experiment, and the amount of food eaten by the lake whitefish during the experiment was tracked. Using these measurements, net trophic transfer efficiency (??) from the rainbow smelt to the lake whitefish in each of the four tanks was calculated for each of the 40 PCB congeners. Results showed that ?? decreased exponentially as log KOW for the congeners increased from 6 to 8. Further, ?? averaged 0.70 for the tetrachloro congeners but averaged only 0.45 for the higher chlorinated congeners. ?? 2008 SETAC.

Lactational Transfer of Polychlorinated-Biphenyls (PCBs) and Other Organochlorines in St. Lawrence Beluga Whales (Delphinapterus leucas).

PubMed

Cadieux, Marc A; Muir, Derek C G; Béland, Pierre; Hickie, Brendan E

2016-01-01

This study uses an individual-based contaminant bioaccumulation model for marine mammals to explore factors controlling the transfer of PCBs from mother to calf via nursing in beluga from the St. Lawrence Estuary. Beluga blubber samples (n = 46), along with four matched milk samples from stranded animals over the 1986-1994 period were used for comparison with modelled results. Based on 68 POPs, including 48 PCBs and 20 other organochlorine compounds, milk:blubber ratios were 0.65 between log K OW 3-6.5, then decreased to 0.1 at log K OW 8. Model simulations based on this relationship indicated females were transferring PCBs that were relatively very hydrophobic and highly chlorinated less readily than their lower chlorinated counterparts, resulting in an enriched concentration of very hydrophobic congeners in nursing females relative to adult males. There was very good agreement between observed and modelled male:female PCB concentration ratios. Four females within our dataset (15 %) had male-like ΣPCB concentrations as well as male-like congener profiles, suggesting that these individuals may have had a reduced or limited nursing history.

Distribution and Bioconcentration of Polycyclic Aromatic Hydrocarbons in Surface Water and Fishes

PubMed Central

Li, Haiyan; Ran, Yong

2012-01-01

To examine spatial distribution and bioconcentration of PAHs, water and fish samples were collected from Pearl River Delta in summer and spring, respectively. Particulate organic carbon, dissolved organic carbon, biodegradable DOC (BDOC), and chlorophyll a were measured. PAHs were dominated by 2- and 3-ring compounds in the water and SPM samples. Aqueous and solid-phase PAHs, respectively, showed significant correlations with total organic matter (TOC) in SPM or dissolved organic matter (DOC) in the water. The in-situ partitioning coefficients (logK oc, mL/g) for the samples were observed to be related to logK ow, implying that the hydrophobicity of PAHs is a critical factor in their distribution. It was also observed that BCF increased with the increasing K ow in the viscera of tilapia (logBCF = 0.507logK ow − 1.368, r = 0.883). However, most of the observed log BCF values in other different fish tissues at first increased with the increasing of log K ow, then reached a maximum value when logK ow is between 5 and 7, and then decreased when logK ow is higher than 7, indicating that the value of BCF may vary due to the diversity of fish species. PMID:23365526

Estimation of soil organic partition coefficients: from retention factors measured by soil column chromatography with water as eluent.

PubMed

Xu, Feng; Liang, Xinmiao; Lin, Bingcheng; Schramm, Karl-Werner; Kettrup, Antonius

2002-08-30

The retention factors (k) of 104 hydrophobic organic chemicals (HOCs) were measured in soil column chromatography (SCC) over columns filled with three naturally occurring reference soils and eluted with Milli-Q water. A novel method for the estimation of soil organic partition coefficient (Koc) was developed based on correlations with k in soil/water systems. Strong log Koc versus log k correlations (r>0.96) were found. The estimated Koc values were in accordance with the literature values with a maximum deviation of less than 0.4 log units. All estimated Koc values from three soils were consistent with each other. The SCC approach is promising for fast screening of a large number of chemicals in their environmental applications.

Protein and lipid binding parameters in rainbow trout (Oncorhynchus mykiss) blood and liver fractions to extrapolate from an in vitro metabolic degradation assay to in vivo bioaccumulation potential of hydrophobic organic chemicals.

PubMed

Escher, Beate I; Cowan-Ellsberry, Christina E; Dyer, Scott; Embry, Michelle R; Erhardt, Susan; Halder, Marlies; Kwon, Jung-Hwan; Johanning, Karla; Oosterwijk, Mattheus T T; Rutishauser, Sibylle; Segner, Helmut; Nichols, John

2011-07-18

Binding of hydrophobic chemicals to colloids such as proteins or lipids is difficult to measure using classical microdialysis methods due to low aqueous concentrations, adsorption to dialysis membranes and test vessels, and slow kinetics of equilibration. Here, we employed a three-phase partitioning system where silicone (polydimethylsiloxane, PDMS) serves as a third phase to determine partitioning between water and colloids and acts at the same time as a dosing device for hydrophobic chemicals. The applicability of this method was demonstrated with bovine serum albumin (BSA). Measured binding constants (K(BSAw)) for chlorpyrifos, methoxychlor, nonylphenol, and pyrene were in good agreement with an established quantitative structure-activity relationship (QSAR). A fifth compound, fluoxypyr-methyl-heptyl ester, was excluded from the analysis because of apparent abiotic degradation. The PDMS depletion method was then used to determine partition coefficients for test chemicals in rainbow trout (Oncorhynchus mykiss) liver S9 fractions (K(S9w)) and blood plasma (K(bloodw)). Measured K(S9w) and K(bloodw) values were consistent with predictions obtained using a mass-balance model that employs the octanol-water partition coefficient (K(ow)) as a surrogate for lipid partitioning and K(BSAw) to represent protein binding. For each compound, K(bloodw) was substantially greater than K(S9w), primarily because blood contains more lipid than liver S9 fractions (1.84% of wet weight vs 0.051%). Measured liver S9 and blood plasma binding parameters were subsequently implemented in an in vitro to in vivo extrapolation model to link the in vitro liver S9 metabolic degradation assay to in vivo metabolism in fish. Apparent volumes of distribution (V(d)) calculated from the experimental data were similar to literature estimates. However, the calculated binding ratios (f(u)) used to relate in vitro metabolic clearance to clearance by the intact liver were 10 to 100 times lower than values used in previous modeling efforts. Bioconcentration factors (BCF) predicted using the experimental binding data were substantially higher than the predicted values obtained in earlier studies and correlated poorly with measured BCF values in fish. One possible explanation for this finding is that chemicals bound to proteins can desorb rapidly and thus contribute to metabolic turnover of the chemicals. This hypothesis remains to be investigated in future studies, ideally with chemicals of higher hydrophobicity. © 2011 American Chemical Society

Investigation of enteric adenovirus and poliovirus removal by coagulation processes and suitability of bacteriophages MS2 and φX174 as surrogates for those viruses.

PubMed

Shirasaki, N; Matsushita, T; Matsui, Y; Marubayashi, T; Murai, K

2016-09-01

We evaluated the removal of enteric adenovirus (AdV) type 40 and poliovirus (PV) type 1 by coagulation, using water samples from 13 water sources for drinking water treatment plants in Japan. The behaviors of two widely accepted enteric virus surrogates, bacteriophages MS2 and φX174, were compared with the behaviors of AdV and PV. Coagulation with polyaluminum chloride (PACl, basicity 1.5) removed AdV and PV from virus-spiked source waters: the infectious AdV and PV removal ratios evaluated by means of a plaque-forming-unit method were 0.1-1.4-log10 and 0.5-2.4-log10, respectively. A nonsulfated high-basicity PACl (basicity 2.1) removed infectious AdV and PV more efficiently than did other commercially available PACls (basicity 1.5-2.1), alum, and ferric chloride. The MS2 removal ratios tended to be larger than those of AdV and PV, partly because of differences in the hydrophobicities of the virus particles and the sensitivity of the virus to the virucidal activity of PACl; the differences in removal ratios were not due to differences in the surface charges of the virus particles. MS2, which was more hydrophobic than the other viruses, was inactivated during coagulation with PACl. Therefore, MS2 does not appear to be an appropriate surrogate for AdV and PV during coagulation. In contrast, because φX174, like AdV and PV, was not inactivated during coagulation, and because the hydrophobicity of φX174 was similar to or somewhat lower than the hydrophobicities of AdV and PV, the φX174 removal ratios tended to be similar to or somewhat smaller than those of the enteric viruses. Therefore, φX174 is a potential conservative surrogate for AdV and PV during coagulation. In summary, the surface hydrophobicity of virus particles and the sensitivity of the virus to the virucidal activity of the coagulant are probably important determinants of the efficiency of virus removal during coagulation. Copyright © 2016 Elsevier B.V. All rights reserved.

Influence of contaminant burial depth on the bioaccumulation of PCBs and PBDEs by two benthic invertebrates (Monoporeia affinis and Marenzelleria spp.).

PubMed

Josefsson, Sarah; Leonardsson, Kjell; Gunnarsson, Jonas S; Wiberg, Karin

2011-11-01

The bioaccumulation of buried polychlorinated biphenyls (PCBs) and polybrominated diphenyl ethers (PBDEs) added to specific depths in sediment (2.0-2.5, 5.0-5.5 and 10.0-10.5cm) was studied in two infaunal species with similar feeding habits (surface deposit-feeders) but different bioturbation modes. The deep-burrowing polychaetes Marenzelleria spp. (Mz) displayed up to 36 times higher tissue concentrations of buried (spiked) contaminants than the surface-dwelling biodiffusing amphipod Monoporeia affinis. The differences in bioaccumulation were most pronounced for less hydrophobic contaminants due to the bioirrigating activity of Mz. Contaminants buried at shallow depths displayed higher accumulation than more deeply buried contaminants. In contrast, the bioaccumulation of unspiked (native) contaminants with a uniform vertical distribution in the sediment was similar between the species. For Mz, the BSAFs increased with increased K(OW) for the uniformly distributed contaminants, but decreased for the buried contaminants, which indicates that the dominant uptake routes of the buried contaminants can differ from the uniformly distributed contaminants. The surface sediment concentration of buried contaminants increased in Mz treatments, showing that Mz bioturbation can remobilize historically buried contaminants to the biologically active surface layer and increase the exposure for surface-dwelling species. Copyright © 2011 Elsevier Ltd. All rights reserved.

Estimates of Octanol-Water Partitioning for Thousands of Dissolved Organic Species in Oil Sands Process-Affected Water.

PubMed

Zhang, Kun; Pereira, Alberto S; Martin, Jonathan W

2015-07-21

In this study, the octanol-water distribution ratios (DOW, that is, apparent KOW at pH 8.4) of 2114 organic species in oil sands process-affected water were estimated by partitioning to polydimethylsiloxane (PDMS) coated stir bars and analysis by ultrahigh resolution orbitrap mass spectrometry in electrospray positive ((+)) and negative ((-)) ionization modes. At equilibrium, the majority of species in OSPW showed negligible partitioning to PDMS (i.e., DOW <1), however estimated DOW's for some species ranged up to 100,000. Most organic acids detected in ESI- had negligible partitioning, although some naphthenic acids (O2(-) species) had estimated DOW ranging up to 100. Polar neutral and basic compounds detected in ESI+ generally partitioned to PDMS to a greater extent than organic acids. Among these species, DOW was greatest among 3 groups: up to 1000 for mono-oxygenated species (O(+) species), up to 127,000 for NO(+) species, and up to 203,000 for SO(+) species. A positive relationship was observed between DOW and carbon number, and a negative relationship was observed with the number of double bonds (or rings). The results highlight that nonacidic compounds in OSPW are generally more hydrophobic than naphthenic acids and that some may be highly bioaccumulative and contribute to toxicity.

How do PDMS-coated stir bars used as passive samplers integrate concentration peaks of pesticides in freshwater?

PubMed

Assoumani, A; Margoum, C; Lombard, A; Guillemain, C; Coquery, M

2017-03-01

Passive samplers are theoretically capable of integrating variations of concentrations of micropollutants in freshwater and providing accurate average values. However, this property is rarely verified and quantified experimentally. In this study, we investigated, in controlled conditions, how the polydimethylsiloxane-coated stir bars (passive Twisters) can integrate fluctuating concentrations of 20 moderately hydrophilic to hydrophobic pesticides (2.18 < Log K ow  < 5.51). In the first two experiments, we studied the pesticide accumulation in the passive Twisters during high concentration peaks of various durations in tap water. We then followed their elimination from the passive Twisters placed in non-contaminated water (experiment no. 1) or in water spiked at low concentrations (experiment no. 2) for 1 week. In the third experiment, we assessed the accuracy of the time-weighted average concentrations (TWAC) obtained from the passive Twisters exposed for 4 days to several concentration variation scenarios. We observed little to no elimination of hydrophobic pesticides from the passive Twisters placed in non-contaminated water and additional accumulation when placed in water spiked at low concentrations. Moreover, passive Twisters allowed determining accurate TWAC (accuracy, determined by TWAC-average measured concentrations ratios, ranged from 82 to 127 %) for the pesticides with Log K ow higher than 4.2. In contrast, fast and large elimination was observed for the pesticides with Log K ow lower than 4.2 and poorer TWAC accuracy (ranging from 32 to 123 %) was obtained.

Evaluation of ecotoxicological effects of benzophenone UV filters: Luminescent bacteria toxicity, genotoxicity and hormonal activity.

PubMed

Zhang, Qiuya; Ma, Xiaoyan; Dzakpasu, Mawuli; Wang, Xiaochang C

2017-08-01

The widespread use of organic ultraviolet (UV) filters in personal care products raises concerns about their potentially hazardous effects on human and ecosystem health. In this study, the toxicities of four commonly used benzophenones (BPs) UV filters including benzophenone (BP), 2-Hydroxybenzophenone (2HB), 2-Hydroxy-4-methoxybenzophenone (BP3), and 2-Hydroxy-4-methoxybenzophenone-5-sulfonicacid (BP4) in water were assayed in vitro using Vibrio fischeri, SOS/umu assay, and yeast estrogen screen (YES) assay, as well as in vivo using zebrafish larvae. The results showed that the luminescent bacteria toxicity, expressed as logEC 50 , increased with the lipophilicity (logKow) of BPs UV filters. Especially, since 2HB, BP3 and BP4 had different substituent groups, namely -OH, -OCH 3 and -SO 3 H, respectively, these substituent functional groups had a major contribution to the lipophilicity and acute toxicity of these BPs. Similar tendency was observed for the genotoxicity, expressed as the value of induction ratio=1.5. Moreover, all the target BPs UV filters showed estrogenic activity, but no significant influences of lipophilicity on the estrogenicity were observed, with BP3 having the weakest estrogenic efficiency in vitro. Although BP3 displayed no noticeable adverse effects in any in vitro assays, multiple hormonal activities were observed in zebrafish larvae including estrogenicity, anti-estrogenicity and anti-androgenicity by regulating the expression of target genes. The results indicated potential hazardous effects of BPs UV filters and the importance of the combination of toxicological evaluation methods including in vitro and in vivo assays. Copyright © 2017 Elsevier Inc. All rights reserved.

Determination of reversed-phase high performance liquid chromatography based octanol-water partition coefficients for neutral and ionizable compounds: Methodology evaluation.

PubMed

Liang, Chao; Qiao, Jun-Qin; Lian, Hong-Zhen

2017-12-15

Reversed-phase liquid chromatography (RPLC) based octanol-water partition coefficient (logP) or distribution coefficient (logD) determination methods were revisited and assessed comprehensively. Classic isocratic and some gradient RPLC methods were conducted and evaluated for neutral, weak acid and basic compounds. Different lipophilicity indexes in logP or logD determination were discussed in detail, including the retention factor logk w corresponding to neat water as mobile phase extrapolated via linear solvent strength (LSS) model from isocratic runs and calculated with software from gradient runs, the chromatographic hydrophobicity index (CHI), apparent gradient capacity factor (k g ') and gradient retention time (t g ). Among the lipophilicity indexes discussed, logk w from whether isocratic or gradient elution methods best correlated with logP or logD. Therefore logk w is recommended as the preferred lipophilicity index for logP or logD determination. logk w easily calculated from methanol gradient runs might be the main candidate to replace logk w calculated from classic isocratic run as the ideal lipophilicity index. These revisited RPLC methods were not applicable for strongly ionized compounds that are hardly ion-suppressed. A previously reported imperfect ion-pair RPLC method was attempted and further explored for studying distribution coefficients (logD) of sulfonic acids that totally ionized in the mobile phase. Notably, experimental logD values of sulfonic acids were given for the first time. The IP-RPLC method provided a distinct way to explore logD values of ionized compounds. Copyright © 2017 Elsevier B.V. All rights reserved.

Amino Acid Block Copolymers with Broad Antimicrobial Activity and Barrier Properties.

PubMed

Bevilacqua, Michael P; Huang, Daniel J; Wall, Brian D; Lane, Shalyn J; Edwards, Carl K; Hanson, Jarrod A; Benitez, Diego; Solomkin, Joseph S; Deming, Timothy J

2017-10-01

Antimicrobial properties of a long-chain, synthetic, cationic, and hydrophobic amino acid block copolymer are reported. In 5 and 60 min time-kill assays, solutions of K 100 L 40 block copolymers (poly(l-lysine·hydrochloride) 100 -b-poly(l-leucine) 40 ) at concentrations of 10-100 µg mL -1 show multi-log reductions in colony forming units of Gram-positive and Gram-negative bacteria, as well as yeast, including multidrug-resistant strains. Driven by association of hydrophobic segments, K 100 L 40 copolymers form viscous solutions and self-supporting hydrogels in water at concentrations of 1 and 2 wt%, respectively. These K 100 L 40 preparations provide an effective barrier to microbial contamination of wounds, as measured by multi-log decreases of tissue-associated bacteria with deliberate inoculation of porcine skin explants, porcine open wounds, and rodent closed wounds with foreign body. Based on these findings, amino acid copolymers with the features of K 100 L 40 can combine potent, direct antimicrobial activity and barrier properties in one biopolymer for a new approach to prevention of wound infections. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Membrane-assisted extraction of monoterpenes: from in silico solvent screening towards biotechnological process application

PubMed Central

2018-01-01

This work focuses on the process development of membrane-assisted solvent extraction of hydrophobic compounds such as monoterpenes. Beginning with the choice of suitable solvents, quantum chemical calculations with the simulation tool COSMO-RS were carried out to predict the partition coefficient (logP) of (S)-(+)-carvone and terpinen-4-ol in various solvent–water systems and validated afterwards with experimental data. COSMO-RS results show good prediction accuracy for non-polar solvents such as n-hexane, ethyl acetate and n-heptane even in the presence of salts and glycerol in an aqueous medium. Based on the high logP value, n-heptane was chosen for the extraction of (S)-(+)-carvone in a lab-scale hollow-fibre membrane contactor. Two operation modes are investigated where experimental and theoretical mass transfer values, based on their related partition coefficients, were compared. In addition, the process is evaluated in terms of extraction efficiency and overall product recovery, and its biotechnological application potential is discussed. Our work demonstrates that the combination of in silico prediction by COSMO-RS with membrane-assisted extraction is a promising approach for the recovery of hydrophobic compounds from aqueous solutions. PMID:29765654

Rhamnolipid CMC prediction.

PubMed

Kłosowska-Chomiczewska, I E; Mędrzycka, K; Hallmann, E; Karpenko, E; Pokynbroda, T; Macierzanka, A; Jungnickel, C

2017-02-15

Relationships between the purity, pH, hydrophobicity (logK ow ) of the carbon substrate, and the critical micelle concentration (CMC) of rhamnolipid type biosurfactants (RL) were investigated using a quantitative structure-property relationship (QSPR) approach and are presented here for the first time. Measured and literature CMC values of 97 RLs, representing biosurfactants at different stages of purification, were considered. An arbitrary scale for RLs purity was proposed and used in the modelling. A modified evolutionary algorithm was used to create clusters of equations to optimally describe the relationship between CMC and logK ow , pH and purity (the optimal equation had an R 2 of 0.8366). It was found that hydrophobicity of the carbon substrate used for the biosynthesis of the RL had the most significant influence on the final CMC of the RL. Purity of the RLs was also found to have a significant impact, where generally the less pure the RL the higher the CMC. These results were in accordance with our experimental data. Therefore, our model equation may be used for controlling the biosynthesis of biosurfactants with properties targeted for specific applications. Copyright © 2016 Elsevier Inc. All rights reserved.

Lipophilicity assessment of basic drugs (log P(o/w) determination) by a chromatographic method.

PubMed

Pallicer, Juan M; Sales, Joaquim; Rosés, Martí; Ràfols, Clara; Bosch, Elisabeth

2011-09-16

A previously reported chromatographic method to determine the 1-octanol/water partition coefficient (log P(o/w)) of organic compounds is used to estimate the hydrophobicity of bases, mainly commercial drugs with diverse chemical nature and pK(a) values higher than 9. For that reason, mobile phases buffered at high pH to avoid the ionization of the solutes and three different columns (Phenomenex Gemini NX, Waters XTerra RP-18 and Waters XTerra MS C(18)) with appropriate alkaline-resistant stationary phases have been used. Non-ionizable substances studied in previous works were also included in the set of compounds to evaluate the consistency of the method. The results showed that all the columns provide good estimations of the log P(o/w) for most of the compounds included in this study. The Gemini NX column has been selected to calculate log P(o/w) values of the set of studied drugs, and really good correlations between the determined log P(o/w) values and those considered as reference were obtained, proving the ability of the procedure for the lipophilicity assessment of bioactive compounds with very different structures and functionalities. Copyright © 2011 Elsevier B.V. All rights reserved.

Sediment toxicity identification evaluation (TIE) studies at marine sites suspected of ordnance contamination

USGS Publications Warehouse

Carr, R.S.; Nipper, M.; Biedenbach, J.M.; Hooten, R.L.; Miller, K.; Saepoff, S.

2001-01-01

A sediment quality assessment survey and subsequent toxicity identification evaluation (TIE) study was conducted at several sites in Puget Sound, Washington. The sites were previously suspected of contamination with ordnance compounds. The initial survey employed sea urchin porewater toxicity tests to locate the most toxic stations. Sediments from the most toxic stations were selected for comprehensive chemical analyses. Based on the combined information from the toxicity and chemical data, three adjacent stations in Ostrich Bay were selected for the TIE study. The results of the phase I TIE suggested that organics and metals were primarily responsible for the observed toxicity in the sea urchin fertilization test. In addition to these contaminants, ammonia was also contributing to the toxicity for the sea urchin embryological development test. The phase II TIE study isolated the majority of the toxicity in the fraction containing nonpolar organics with high log Kow, but chemical analyses failed to identify a compound present at a concentration high enough to be responsible for the observed toxicity. The data suggest that some organic or organometallic contaminant(s) that were not included in the comprehensive suite of chemical analyses caused the observed toxicological responses.

Net trophic transfer efficiencies of polychlorinated biphenyl congeners to lake trout (Salvelinus namaycush) from its prey

USGS Publications Warehouse

Madenjian, Charles P.; David, Solomon R.; Rediske, Richard R.; O’Keefe, James P.

2012-01-01

Lake trout (Salvelinus namaycush) were fed bloater (Coregonus hoyi) in eight laboratory tanks over a 135-d experiment. At the start of the experiment, four to nine fish in each tank were sacrificed, and the concentrations of 75 polychlorinated biphenyl (PCB) congeners within these fish were determined. Polychlorinated biphenyl congener concentrations were also determined in the 10 lake trout remaining in each of the eight tanks at the end of the experiment as well as in the bloater fed to the lake trout. Each lake trout was weighed at the start and the end of the experiment, and the amount of food eaten by the lake trout was recorded. Using these measurements, net trophic transfer efficiency (γ) from the bloater to the lake trout in each of the eight tanks was calculated for each of the 75 congeners. Results showed that γ did not vary significantly with the degree of chlorination of the PCB congeners, and γ averaged 0.66 across all congeners. However,γ did show a slight, but significant, decrease as logKOW increased from 6.0 to 8.2. Activity level of the lake trout did not have a significant effect on γ.

Silicone wristbands as personal passive samplers.

PubMed

O'Connell, Steven G; Kincl, Laurel D; Anderson, Kim A

2014-03-18

Active-sampling approaches are commonly used for personal monitoring, but are limited by energy usage and data that may not represent an individual's exposure or bioavailable concentrations. Current passive techniques often involve extensive preparation, or are developed for only a small number of targeted compounds. In this work, we present a novel application for measuring bioavailable exposure with silicone wristbands as personal passive samplers. Laboratory methodology affecting precleaning, infusion, and extraction were developed from commercially available silicone, and chromatographic background interference was reduced after solvent cleanup with good extraction efficiency (>96%). After finalizing laboratory methods, 49 compounds were sequestered during an ambient deployment which encompassed a diverse set of compounds including polycyclic aromatic hydrocarbons (PAHs), consumer products, personal care products, pesticides, phthalates, and other industrial compounds ranging in log K(ow) from -0.07 (caffeine) to 9.49 (tris(2-ethylhexyl) phosphate). In two hot asphalt occupational settings, silicone personal samplers sequestered 25 PAHs during 8- and 40-h exposures, as well as 2 oxygenated-PAHs (benzofluorenone and fluorenone) suggesting temporal sensitivity over a single work day or week (p < 0.05, power =0.85). Additionally, the amount of PAH sequestered differed between worksites (p < 0.05, power = 0.99), suggesting spatial sensitivity using this novel application.

Mixture toxicity of the anti-inflammatory drugs diclofenac, ibuprofen, naproxen, and acetylsalicylic acid.

PubMed

Cleuvers, Michael

2004-11-01

The ecotoxicity of the nonsteroidal anti-inflammatory drugs (NSAIDs) diclofenac, ibuprofen, naproxen, and acetylsalicylic acid (ASA) has been evaluated using acute Daphnia and algal tests. Toxicities were relatively low, with half-maximal effective concentration (EC50) values obtained using Daphnia in the range from 68 to 166 mg L(-1) and from 72 to 626 mg L(-1) in the algal test. Acute effects of these substances seem to be quite improbable. The quantitative structure-activity relationships (QSAR) approach showed that all substances act by nonpolar narcosis; thus, the higher the n-octanol/water partitioning coefficient (log Kow) of the substances, the higher is their toxicity. Mixture toxicity of the compounds could be accurately predicted using the concept of concentration addition. Toxicity of the mixture was considerable, even at concentrations at which the single substances showed no or only very slight effects, with some deviations in the Daphnia test, which could be explained by incompatibility of the very steep dose-response curves and the probit analysis of the data. Because pharmaceuticals in the aquatic environment occur usually as mixtures, an accurate prediction of the mixture toxicity is indispensable for environmental risk assessment.

Selective removal of organochlorine pesticides (OCPs) from aqueous solution by triolein-embedded composite adsorbent.

PubMed

Ru, J; Liu, H J; Qu, J H; Wang, A M; Dai, R H; Wang, Z J

2007-01-01

A novel composite adsorbent (CA-T) was used for the selective removal of organochlorine pesticides (OCPs) from aqueous solution. The adsorbent was composed of the supporting activated carbon and the surrounding triolein-embedded cellulose acetate membrane. Scanning electron microscopy (SEM), N2 adsorption isotherms and fluorescence methods were used to characterize the physicochemical properties of CA-T. Triolein was perfectly embedded in the cellulose acetate membrane and deposited on the surface of activated carbon. The adsorbent was stable in water and no triolein leakage was detected during the test periods. Some organochlorine pesticides (OCPs), such as dieldrin, endrin, aldrin, and heptachlor epoxide, were used as model contaminants and removed by CA-T in laboratory batch experiments. The adsorption isotherm followed the Freundlich equation and the kinetic data fitted well to the pseudo-second-order reaction model. Results also indicated that CA-T appeared to be a promising adsorbent with good selectivity and satisfactory removal rate for lipophilic OCPs from aqueous solutions when present in trace amounts. The adsorption rate and removal efficiency for lipophilic OCPs were positively related to their octanol-water partition coefficients (log K(ow)). Lower residual concentrations of OCPs were achieved when compared to granular activated carbon (GAC).

Tyrosine-derived Polycarbonate-silica Xerogel Nanocomposites for Controlled Drug Delivery

DTIC Science & Technology

2013-02-05

of relatively hydrophobic compounds , while for the hydrophilic bupivacaine logP = 0.30 [52] and PSA = 32.3[51]. The relatively small difference in ... of 5–20 times those of the co-polymers or of composites made with micron scale silica particles. Increasing the fraction of xerogel in the ...ability and viscoelasticity of biodegradable organic polymers with the mechanical strength of biodegradable

Relationships between hydrophobicity, reactivity, accumulation and peripheral nerve toxicity of a series of platinum drugs

PubMed Central

Screnci, D; McKeage, M J; Galettis, P; Hambley, T W; Palmer, B D; Baguley, B C

2000-01-01

Previous work has shown platinum drugs to differ in their effects on the peripheral nervous system. To test whether their differential toxicity was due to differences in their partitioning into the peripheral nervous system, we correlated the hydrophobicity, reactivity, tissue accumulation and neurotoxicity of a series of eight platinum analogues. Neurotoxicity was detected by measuring sensory nerve conduction velocity (SNCV) in Wistar rats treated twice per week at the maximum tolerated dose. Tissue platinum concentrations were measured by inductively coupled plasma mass spectrometry. Hydrophobicity (log P) was measured using an octanol-aqueous shake-flask method. The half-life of platinum drug binding to plasma proteins in vitro was determined. The cumulative dose causing altered SNCV ranged from 15 to > 2050 μmol kg−1. Ranking of the compounds by their neurotoxic potency in rats (oxaliplatin >R,R -(DACH)PtC4> ormaplatin >S,S -(DACH)PtCl4>S,S -(DACH)Pt oxalato > cisplatin > carboplatin > JM216) correlated with the frequency of neurotoxicity in patients (r> 0.99;P< 0.05). Ranking the compounds by their peripheral nerve accumulation was cisplatin > carboplatin > oxaliplatin >R,R -(DACH)PtCl4≈S,S -(DACH)PtCl4and did not correlate with neurotoxicity. Log P ranged from – 2.53 to –0.16 but did not correlate with neurotoxicity. Log P correlated inversely with platinum accumulation in dorsal root ganglia (r2= 0.99;P = 0.04), sural nerve (r2= 0.85;P = 0.025), sciatic nerve (r2= 0.98;P = 0.0012), spinal cord (r2= 0.97, P = 0.018) and brain (r2= 0.98, P = 0.001). Reactivity correlated with neurotoxicity potency in rats (r2= 0.89, P = 0.0005) and with the frequency of neurotoxicity in patients (r2= 0.99, P = 0.0002). The hydrophilicity of platinum drugs correlates with platinum sequestration in the peripheral nervous system but not with neurotoxicity. Differences in the reactivity of platinum complexes accounts for some of the variation in their neurotoxicity. © 2000 Cancer Research Campaign PMID:10732773

Development of TLSER model and QSAR model for predicting partition coefficients of hydrophobic organic chemicals between low density polyethylene film and water.

PubMed

Liu, Huihui; Wei, Mengbi; Yang, Xianhai; Yin, Cen; He, Xiao

2017-01-01

Partition coefficients are vital parameters for measuring accurately the chemicals concentrations by passive sampling devices. Given the wide use of low density polyethylene (LDPE) film in passive sampling, we developed a theoretical linear solvation energy relationship (TLSER) model and a quantitative structure-activity relationship (QSAR) model for the prediction of the partition coefficient of chemicals between LDPE and water (K pew ). For chemicals with the octanol-water partition coefficient (log K ow ) <8, a TLSER model with V x (McGowan volume) and qA - (the most negative charge on O, N, S, X atoms) as descriptors was developed, but the model had relatively low determination coefficient (R 2 ) and cross-validated coefficient (Q 2 ). In order to further explore the theoretical mechanisms involved in the partition process, a QSAR model with four descriptors (MLOGP (Moriguchi octanol-water partition coeff.), P_VSA_s_3 (P_VSA-like on I-state, bin 3), Hy (hydrophilic factor) and NssO (number of atoms of type ssO)) was established, and statistical analysis indicated that the model had satisfactory goodness-of-fit, robustness and predictive ability. For chemicals with log K OW >8, a TLSER model with V x and a QSAR model with MLOGP as descriptor were developed. This is the first paper to explore the models for highly hydrophobic chemicals. The applicability domain of the models, characterized by the Euclidean distance-based method and Williams plot, covered a large number of structurally diverse chemicals, which included nearly all the common hydrophobic organic compounds. Additionally, through mechanism interpretation, we explored the structural features those governing the partition behavior of chemicals between LDPE and water. Copyright © 2016 Elsevier B.V. All rights reserved.

Brownian dynamics simulation of amphiphilic block copolymers with different tail lengths, comparison with theory and comicelles.

PubMed

Hafezi, Mohammad-Javad; Sharif, Farhad

2015-11-01

Study on the effect of amphiphilic copolymers structure on their self assembly is an interesting subject, with important applications in the area of drug delivery and biological system treatments. Brownian dynamics simulations were performed to study self-assembly of the linear amphiphilic block copolymers with the same hydrophilic head, but hydrophobic tails of different lengths. Critical micelle concentration (CMC), gyration radius distribution, micelle size distribution, density profiles of micelles, shape anisotropy, and dynamics of micellization were investigated as a function of tail length. Simulation results were compared with predictions from theory and simulation for mixed systems of block copolymers with long and short hydrophobic tail, reported in our previous work. Interestingly, the equilibrium structural and dynamic parameters of pure and mixed block copolymers were similarly dependant on the intrinsic/apparent hydrophobic block length. Log (CMC) was, however; proportional to the tail length and had a different behavior compared to the mixed system. The power law scaling relation of equilibrium structural parameters for amphiphilic block copolymers predicts the same dependence for similar hydrophobic tail lengths, but the power law prediction of CMC is different, which is due to its simplifying assumptions as discussed here. Copyright © 2015 Elsevier Inc. All rights reserved.

Test methods for estimating the efficacy of the fast-acting disinfectant peracetic acid on surfaces of personal protective equipment.

PubMed

Lemmer, K; Howaldt, S; Heinrich, R; Roder, A; Pauli, G; Dorner, B G; Pauly, D; Mielke, M; Schwebke, I; Grunow, R

2017-11-01

The work aimed at developing and evaluating practically relevant methods for testing of disinfectants on contaminated personal protective equipment (PPE). Carriers were prepared from PPE fabrics and contaminated with Bacillus subtilis spores. Peracetic acid (PAA) was applied as a suitable disinfectant. In method 1, the contaminated carrier was submerged in PAA solution; in method 2, the contaminated area was covered with PAA; and in method 3, PAA, preferentially combined with a surfactant, was dispersed as a thin layer. In each method, 0·5-1% PAA reduced the viability of spores by a factor of ≥6 log 10 within 3 min. The technique of the most realistic method 3 proved to be effective at low temperatures and also with a high organic load. Vaccinia virus and Adenovirus were inactivated with 0·05-0·1% PAA by up to ≥6 log 10 within 1 min. The cytotoxicity of ricin was considerably reduced by 2% PAA within 15 min of exposure. PAA/detergent mixture enabled to cover hydrophobic PPE surfaces with a thin and yet effective disinfectant layer. The test methods are objective tools for estimating the biocidal efficacy of disinfectants on hydrophobic flexible surfaces. © 2017 The Society for Applied Microbiology.

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.

Accumulation of current-use and organochlorine pesticides in crab embryos from Northern California, USA

USGS Publications Warehouse

Smalling, Kelly L.; Morgan, Steven; Kuivila, Kathryn K.

2010-01-01

Invertebrates have long been used as resident sentinels for assessing ecosystem health and productivity. The shore crabs, Hemigrapsus oregonensis and Pachygrapsus crassipes, are abundant in estuaries and beaches throughout northern California, USA and have been used as indicators of habitat conditions in several salt marshes. The overall objectives of the present study were to conduct a lab-based study to test the accumulation of current-use pesticides, validate the analytical method and to analyze field-collected crabs for a suite of 74 current-use and legacy pesticides. A simple laboratory uptake study was designed to determine if embryos could bioconcentrate the herbicide molinate over a 7-d period. At the end of the experiment, embryos were removed from the crabs and analyzed by gas chromatography/mass spectrometry. Although relatively hydrophilic (log KOW of 2.9), molinate did accumulate with an estimated bioconcentration factor (log BCF) of approximately 2.5. Following method validation, embryos were collected from two different Northern California salt marshes and analyzed. In field-collected embryos 18 current-use and eight organochlorine pesticides were detected including synthetic pyrethroids and organophosphate insecticides, as well as DDT and its degradates. Lipid-normalized concentrations of the pesticides detected in the field-collected crab embryos ranged from 0.1 to 4 ppm. Pesticide concentrations and profiles in crab embryos were site specific and could be correlated to differences in land-use practices. These preliminary results indicate that embryos are an effective sink for organic contaminants in the environment and have the potential to be good indicators of ecosystem health, especially when contaminant body burden analyses are paired with reproductive impairment assays.

Accumulation of current-use and organochlorine pesticides in crab embryos from northern California, USA.

PubMed

Smalling, Kelly L; Morgan, Steven; Kuivila, Kathryn K

2010-11-01

Invertebrates have long been used as resident sentinels for assessing ecosystem health and productivity. The shore crabs, Hemigrapsus oregonensis and Pachygrapsus crassipes, are abundant in estuaries and beaches throughout northern California, USA and have been used as indicators of habitat conditions in several salt marshes. The overall objectives of the present study were to conduct a lab-based study to test the accumulation of current-use pesticides, validate the analytical method and to analyze field-collected crabs for a suite of 74 current-use and legacy pesticides. A simple laboratory uptake study was designed to determine if embryos could bioconcentrate the herbicide molinate over a 7-d period. At the end of the experiment, embryos were removed from the crabs and analyzed by gas chromatography/mass spectrometry. Although relatively hydrophilic (log K(OW) of 2.9), molinate did accumulate with an estimated bioconcentration factor (log BCF) of approximately 2.5. Following method validation, embryos were collected from two different Northern California salt marshes and analyzed. In field-collected embryos 18 current-use and eight organochlorine pesticides were detected including synthetic pyrethroids and organophosphate insecticides, as well as DDT and its degradates. Lipid-normalized concentrations of the pesticides detected in the field-collected crab embryos ranged from 0.1 to 4 ppm. Pesticide concentrations and profiles in crab embryos were site specific and could be correlated to differences in land-use practices. These preliminary results indicate that embryos are an effective sink for organic contaminants in the environment and have the potential to be good indicators of ecosystem health, especially when contaminant body burden analyses are paired with reproductive impairment assays. © 2010 SETAC.

Assessing the persistence, bioaccumulation potential and toxicity of brominated flame retardants: data availability and quality for 36 alternative brominated flame retardants.

PubMed

Stieger, Greta; Scheringer, Martin; Ng, Carla A; Hungerbühler, Konrad

2014-12-01

Polybrominated diphenylethers (PBDEs) and hexabromocyclododecane (HBCDD) are major brominated flame retardants (BFRs) that are now banned or under restrictions in many countries because of their persistence, bioaccumulation potential and toxicity (PBT properties). However, there is a wide range of alternative BFRs, such as decabromodiphenyl ethane and tribromophenol, that are increasingly used as replacements, but which may possess similar hazardous properties. This necessitates hazard and risk assessments of these compounds. For a set of 36 alternative BFRs, we searched 25 databases for chemical property data that are needed as input for a PBT assessment. These properties are degradation half-life, bioconcentration factor (BCF), octanol-water partition coefficient (Kow), and toxic effect concentrations in aquatic organisms. For 17 of the 36 substances, no data at all were found for these properties. Too few persistence data were available to even assess the quality of these data in a systematic way. The available data for Kow and toxicity show surprisingly high variability, which makes it difficult to identify the most reliable values. We propose methods for systematic evaluations of PBT-related chemical property data that should be performed before data are included in publicly available databases. Using these methods, we evaluated the data for Kow and toxicity in more detail and identified several inaccurate values. For most of the 36 alternative BFRs, the amount and the quality of the PBT-related property data need to be improved before reliable hazard and risk assessments of these substances can be performed. Copyright © 2014 Elsevier Ltd. All rights reserved.

Papain hydrolysis of X-phenyl-N-methanesulfonyl glycinates: a quantitative structure-activity relationship and molecular graphics analysis.

PubMed

Carotti, A; Smith, R N; Wong, S; Hansch, C; Blaney, J M; Langridge, R

1984-02-15

The hydrolysis of 32 X-phenyl-N-methanesulfonyl glycinates by papain was investigated. It was found that the variation in the Michaelis constants could be rationalized by the following correlation equation: log 1/Km = 0.61 pi '3 + 0.46 MR4 + 0.55 sigma + 2.00 with a correlation coefficient of 0.945. In this expression, pi '3 is the hydrophobic constant for the more lipophilic of the two possible meta substituents, MR4 is the molar refractivity of 4-substituents, and sigma is the Hammett constant summed for all substituents. Using this equation, we designed, synthesized, and successfully predicted Km for a new congener intended to maximize binding (1/Km). The interactions involved in enzyme-substrate binding, as characterized by the correlation equation, are interpreted using a computer-constructed color three-dimensional-graphics molecular model of the enzyme active site. The nonenzymatic hydrolysis (both acid and basic) of phenyl hippurates yield rate constants which are well correlated by Hammett equations; however, log k for both acid and alkaline hydrolysis are not linearly related to log 1/Km or log kcat/Km.

Uptake and disposition of select pharmaceuticals by bluegill exposed at constant concentrations in a flow-through aquatic exposure system

USGS Publications Warehouse

Zhao, Jian-Liang; Furlong, Edward T.; Schoenfuss, Heiko L.; Kolpin, Dana W.; Bird, Kyle L.; Feifarek, David J.; Schwab, Eric A.; Ying, Guang-Guo

2017-01-01

The increasing use of pharmaceuticals has led to their subsequent input into and release from wastewater treatment plants, with corresponding discharge into surface waters that may subsequently exert adverse effects upon aquatic organisms. Although the distribution of pharmaceuticals in surface water has been extensively studied, the details of uptake, internal distribution, and kinetic processing of pharmaceuticals in exposed fish have received less attention. For this research, we investigated the uptake, disposition, and toxicokinetics of five pharmaceuticals (diclofenac, methocarbamol, rosuvastatin, sulfamethoxazole, and temazepam) in bluegill sunfish (Lepomis macrochirus) exposed to environmentally relevant concentrations (1000–4000 ng L–1) in a flow-through exposure system. Temazepam and methocarbamol were consistently detected in bluegill biological samples with the highest concentrations in bile of 4, 940, and 180 ng g–1, respectively, while sulfamethoxazole, diclofenac, and rosuvastatin were only infrequently detected. Over 30-day exposures, the relative magnitude of mean concentrations of temazepam and methocarbamol in biological samples generally followed the order: bile ≫ gut > liver and brain > muscle, plasma, and gill. Ranges of bioconcentration factors (BCFs) in different biological samples were 0.71–3960 and 0.13–48.6 for temazepam and methocarbamol, respectively. Log BCFs were statistically positively correlated to pH adjusted log Kow (that is, log Dow), with the strongest relations for liver and brain (r2 = 0.92 and 0.99, respectively), implying that bioconcentration patterns of ionizable pharmaceuticals depend on molecular status, that is, whether a pharmaceutical is un-ionized or ionized at ambient tissue pH. Methocarbamol and temazepam underwent rapid uptake and elimination in bluegill biological compartments with uptake rate constants (Ku) and elimination rate constants (Ke) at 0.0066–0.0330 h–1 and 0.0075–0.0384 h–1, respectively, and half-lives at 18.1–92.4 h. Exposure to mixtures of diclofenac, methocarbamol, sulfamethoxazole, and temazepam had little or no influence on the uptake and elimination rates, suggesting independent multiple uptake and disposition behaviors of pharmaceuticals by fish would occur when exposed to effluent-influenced surface waters.

Summary of Cefic-LRI sponsored workshop: Recent scientific developments in bioaccumulation research

EPA Science Inventory

Current bioaccumulation regulations in most jurisdictions include only the bioconcentration factor (BCF) and the octanol-water partition coefficient (KOW) for screening assessments. Methods for evaluating bioaccumulation continue to evolve and various other metrics have been prop...

Using solid phase micro extraction to determine salting-out (Setschenow) constants for hydrophobic organic chemicals.

PubMed

Jonker, Michiel T O; Muijs, Barry

2010-06-01

With increasing ionic strength, the aqueous solubility and activity of organic chemicals are altered. This so-called salting-out effect causes the hydrophobicity of the chemicals to be increased and sorption in the marine environment to be more pronounced than in freshwater systems. The process can be described with empirical salting-out or Setschenow constants, which traditionally are determined by comparing aqueous solubilities in freshwater and saline water. Aqueous solubilities of hydrophobic organic chemicals (HOCs) however are difficult to determine, which might partly explain the limited size of the existing data base on Setschenow constants for these chemicals. In this paper, we propose an alternative approach for determining the constants, which is based on the use of solid phase micro extraction (SPME) fibers. Partitioning of polycyclic aromatic hydrocarbons (PAHs) to SPME fibers increased about 1.7 times when going from de-ionized water to seawater. From the log-linear relationship between SPME fiber-water partition coefficients and ionic strength, Setschenow constants were derived, which measured on average 0.35 L mol(-1). These values agreed with literature values existing for some of the investigated PAHs and were independent of solute hydrophobicity or molar volume. Based on the present data, SPME seems to be a convenient and suitable alternative technique to determine Setschenow constants for HOCs. Copyright (c) 2010 Elsevier Ltd. All rights reserved.

Adhesion of Bacillus spores and Escherichia coli cells to inert surfaces: role of surface hydrophobicity.

PubMed

Faille, Christine; Jullien, Celine; Fontaine, Francoise; Bellon-Fontaine, Marie-Noelle; Slomianny, Christian; Benezech, Thierry

2002-08-01

The ability of bacterial spores and vegetative cells to adhere to inert surfaces was investigated by means of the number of adherent spores (Bacillus cereus and Bacillus subtilis spores) and Escherichia coli cells and their resistance to cleaning or rinsing procedures (adhesion strength). Six materials (glass, stainless steel, polyethylene high density (PEHD), polyamide-6, polyvinyl chloride, and Teflon) were tested. Slight differences in the number of adherent spores (less than 1 log unit) were observed between materials, but a higher number of adherent E. coli cells was found on the hydrophobic materials PEHD and Teflon. Conversely, the resistance of both B. cereus and B. subtilis spores to a cleaning procedure was significantly affected by the material. Hydrophobic materials were harder to clean. The topography parameter derived from the Abbott-Firestone curve, RVK, and, to a lesser extent, the widely used roughness parameters RA (average roughness) and Rz (maximal roughness), were related to the number of adherent cells. Lastly, the soiling level as well as the adhesion strength were shown to depend largely on the microorganism. The number of adhering B. cereus hydrophobic spores and their resistance to a cleaning procedure were found to be 10 times greater than those of the B. subtilis hydrophilic spores. Escherichia coli was loosely bound to all the materials tested, even after 24 h biofilm formation.

Systems Biology Approach Reveals a Calcium-Dependent Mechanism for Basal Toxicity in Daphnia magna.

PubMed

Antczak, Philipp; White, Thomas A; Giri, Anirudha; Michelangeli, Francesco; Viant, Mark R; Cronin, Mark T D; Vulpe, Chris; Falciani, Francesco

2015-09-15

The expanding diversity and ever increasing amounts of man-made chemicals discharged to the environment pose largely unknown hazards to ecosystem and human health. The concept of adverse outcome pathways (AOPs) emerged as a comprehensive framework for risk assessment. However, the limited mechanistic information available for most chemicals and a lack of biological pathway annotation in many species represent significant challenges to effective implementation of this approach. Here, a systems level, multistep modeling strategy demonstrates how to integrate information on chemical structure with mechanistic insight from genomic studies, and phenotypic effects to define a putative adverse outcome pathway. Results indicated that transcriptional changes indicative of intracellular calcium mobilization were significantly overrepresented in Daphnia magna (DM) exposed to sublethal doses of presumed narcotic chemicals with log Kow ≥ 1.8. Treatment of DM with a calcium ATPase pump inhibitor substantially recapitulated the common transcriptional changes. We hypothesize that calcium mobilization is a potential key molecular initiating event in DM basal (narcosis) toxicity. Heart beat rate analysis and metabolome analysis indicated sublethal effects consistent with perturbations of calcium preceding overt acute toxicity. Together, the results indicate that altered calcium homeostasis may be a key early event in basal toxicity or narcosis induced by lipophilic compounds.

Comparison of Measured and Predicted Bioconcentration Estimates of Pharmaceuticals in Fish Plasma and Prediction of Chronic Risk.

PubMed

Nallani, Gopinath; Venables, Barney; Constantine, Lisa; Huggett, Duane

2016-05-01

Evaluation of the environmental risk of human pharmaceuticals is now a mandatory component in all new drug applications submitted for approval in EU. With >3000 drugs currently in use, it is not feasible to test each active ingredient, so prioritization is key. A recent review has listed nine prioritization approaches including the fish plasma model (FPM). The present paper focuses on comparison of measured and predicted fish plasma bioconcentration factors (BCFs) of four common over-the-counter/prescribed pharmaceuticals: norethindrone (NET), ibuprofen (IBU), verapamil (VER) and clozapine (CLZ). The measured data were obtained from the earlier published fish BCF studies. The measured BCF estimates of NET, IBU, VER and CLZ were 13.4, 1.4, 0.7 and 31.2, while the corresponding predicted BCFs (based log Kow at pH 7) were 19, 1.0, 7.6 and 30, respectively. These results indicate that the predicted BCFs matched well the measured values. The BCF estimates were used to calculate the human: fish plasma concentration ratios of each drug to predict potential risk to fish. The plasma ratio results show the following order of risk potential for fish: NET > CLZ > VER > IBU. The FPM has value in prioritizing pharmaceutical products for ecotoxicological assessments.

Classifying environmental pollutants: Part 3. External validation of the classification system.

PubMed

Verhaar, H J; Solbé, J; Speksnijder, J; van Leeuwen, C J; Hermens, J L

2000-04-01

In order to validate a classification system for the prediction of the toxic effect concentrations of organic environmental pollutants to fish, all available fish acute toxicity data were retrieved from the ECETOC database, a database of quality-evaluated aquatic toxicity measurements created and maintained by the European Centre for the Ecotoxicology and Toxicology of Chemicals. The individual chemicals for which these data were available were classified according to the rulebase under consideration and predictions of effect concentrations or ranges of possible effect concentrations were generated. These predictions were compared to the actual toxicity data retrieved from the database. The results of this comparison show that generally, the classification system provides adequate predictions of either the aquatic toxicity (class 1) or the possible range of toxicity (other classes) of organic compounds. A slight underestimation of effect concentrations occurs for some highly water soluble, reactive chemicals with low log K(ow) values. On the other end of the scale, some compounds that are classified as belonging to a relatively toxic class appear to belong to the so-called baseline toxicity compounds. For some of these, additional classification rules are proposed. Furthermore, some groups of compounds cannot be classified, although they should be amenable to predictions. For these compounds additional research as to class membership and associated prediction rules is proposed.

Plant consumption by grizzly bears reduces biomagnification of salmon-derived polychlorinated biphenyls, polybrominated diphenyl ethers, and organochlorine pesticides.

PubMed

Christensen, Jennie R; Yunker, Mark B; MacDuffee, Misty; Ross, Peter S

2013-04-01

The present study characterizes the uptake and loss of persistent organic pollutants (POPs) in grizzly bears (Ursus arctos horribilis) by sampling and analyzing their terrestrial and marine foods and fecal material from a remote coastal watershed in British Columbia, Canada. The authors estimate that grizzly bears consume 341 to 1,120 µg of polychlorinated biphenyls (PCBs) and 3.9 to 33 µg of polybrominated diphenyl ethers daily in the fall when they have access to an abundant supply of returning salmon. The authors also estimate that POP elimination by grizzly bears through defecation is very low following salmon consumption (typically <2% of intake) but surprisingly high following plant consumption (>100% for PCBs and organochlorine pesticides). Excretion of individual POPs is largely driven by a combination of fugacity (differences between bear and food concentrations) and the digestibility of the food. The results of the present study are substantiated by a principal components analysis, which also demonstrates a strong role for log KOW in governing the excretion of different POPs in grizzly bears. Collectively, the present study's results reveal that grizzly bears experience a vegetation-associated drawdown of POPs previously acquired through the consumption of salmon, to such an extent that net biomagnification is reduced. Copyright © 2013 SETAC.

Silicone Wristbands as Personal Passive Samplers

PubMed Central

2014-01-01

Active-sampling approaches are commonly used for personal monitoring, but are limited by energy usage and data that may not represent an individual’s exposure or bioavailable concentrations. Current passive techniques often involve extensive preparation, or are developed for only a small number of targeted compounds. In this work, we present a novel application for measuring bioavailable exposure with silicone wristbands as personal passive samplers. Laboratory methodology affecting precleaning, infusion, and extraction were developed from commercially available silicone, and chromatographic background interference was reduced after solvent cleanup with good extraction efficiency (>96%). After finalizing laboratory methods, 49 compounds were sequestered during an ambient deployment which encompassed a diverse set of compounds including polycyclic aromatic hydrocarbons (PAHs), consumer products, personal care products, pesticides, phthalates, and other industrial compounds ranging in log Kow from −0.07 (caffeine) to 9.49 (tris(2-ethylhexyl) phosphate). In two hot asphalt occupational settings, silicone personal samplers sequestered 25 PAHs during 8- and 40-h exposures, as well as 2 oxygenated-PAHs (benzofluorenone and fluorenone) suggesting temporal sensitivity over a single work day or week (p < 0.05, power =0.85). Additionally, the amount of PAH sequestered differed between worksites (p < 0.05, power = 0.99), suggesting spatial sensitivity using this novel application. PMID:24548134

Evaluation of 3D-human skin equivalents for assessment of human dermal absorption of some brominated flame retardants.

PubMed

Abdallah, Mohamed Abou-Elwafa; Pawar, Gopal; Harrad, Stuart

2015-11-01

Ethical and technical difficulties inherent to studies in human tissues are impeding assessment of the dermal bioavailability of brominated flame retardants (BFRs). This is further complicated by increasing restrictions on the use of animals in toxicity testing, and the uncertainties associated with extrapolating data from animal studies to humans due to inter-species variations. To overcome these difficulties, we evaluate 3D-human skin equivalents (3D-HSE) as a novel in vitro alternative to human and animal testing for assessment of dermal absorption of BFRs. The percutaneous penetration of hexabromocyclododecanes (HBCD) and tetrabromobisphenol-A (TBBP-A) through two commercially available 3D-HSE models was studied and compared to data obtained for human ex vivo skin according to a standard protocol. No statistically significant differences were observed between the results obtained using 3D-HSE and human ex vivo skin at two exposure levels. The absorbed dose was low (less than 7%) and was significantly correlated with log Kow of the tested BFR. Permeability coefficient values showed increasing dermal resistance to the penetration of γ-HBCD>β-HBCD>α-HBCD>TBBPA. The estimated long lag times (>30 min) suggests that frequent hand washing may reduce human exposure to HBCDs and TBBPA via dermal contact. Copyright © 2015 Elsevier Ltd. All rights reserved.

Large and growing environmental reservoirs of Deca-BDE present an emerging health risk for fish and marine mammals.

PubMed

Ross, Peter S; Couillard, Catherine M; Ikonomou, Michael G; Johannessen, Sophia C; Lebeuf, Michel; Macdonald, Robie W; Tomy, Gregg T

2009-01-01

Polybrominated diphenyl ethers (PBDEs) have been the subject of intense scientific and regulatory scrutiny during recent years. Of the three commercial forms (Penta, Octa and Deca) of PBDEs that have been widely used as flame retardants in textiles, furniture upholstery, plastics, and electronics, only Deca-BDE remains on the general market in North America, while a recent ruling of the European Court spells an impending end to its use in Europe. We review here highlights of aquatic research documenting the rapid emergence of PBDEs as a high priority environmental concern in Canada. PBDEs are being introduced in large quantities to the aquatic environment through sewage discharge and atmospheric deposition. In certain environmental compartments, the single congener BDE-209, the main ingredient in the Deca-BDE formulation, has surpassed the legacy PCBs and DDT as the top contaminant by concentration. Limited biomagnification of BDE-209 in aquatic food webs reflects its high log K(ow) and preferential partitioning into the particle phase. As a result, large environmental reservoirs of BDE-209 are being created in sediments, and these may present a long-term threat to biota: BDE-209 breaks down into more persistent, more bioaccumulative, more toxic, and more mobile PBDE congeners in the environment.

Factors Affecting Transfer of Pyrethroid Residues from Herbal Teas to Infusion and Influence of Physicochemical Properties of Pesticides

PubMed Central

Xiao, Jin-Jing; Li, Yang; Fang, Qing-Kui; Shi, Yan-Hong; Liao, Min; Wu, Xiang-Wei; Hua, Ri-Mao

2017-01-01

The transfer of pesticide residues from herbal teas to their infusion is a subject of particular interest. In this study, a multi-residue analytical method for the determination of pyrethroids (fenpropathrin, beta-cypermethrin, lambda-cyhalothrin, and fenvalerate) in honeysuckle, chrysanthemum, wolfberry, and licorice and their infusion samples was validated. The transfer of pyrethroid residues from tea to infusion was investigated at different water temperatures, tea/water ratios, and infusion intervals/times. The results show that low amounts (0–6.70%) of pyrethroids were transferred under the different tea brewing conditions examined, indicating that the infusion process reduced the pyrethroid content in the extracted liquid by over 90%. Similar results were obtained for the different tea varieties, and pesticides with high water solubility and low octanol–water partition coefficients (log Kow) exhibited high transfer rates. Moreover, the estimated values of the exposure risk to the pyrethroids were in the range of 0.0022–0.33, indicating that the daily intake of the four pyrethroid residues from herbal tea can be regarded as safe. The present results can support the identification of suitable tea brewing conditions for significantly reducing the pesticide residue levels in the infusion. PMID:28973970

Predicting human skin absorption of chemicals: development of a novel quantitative structure activity relationship.

PubMed

Luo, Wen; Medrek, Sarah; Misra, Jatin; Nohynek, Gerhard J

2007-02-01

The objective of this study was to construct and validate a quantitative structure-activity relationship model for skin absorption. Such models are valuable tools for screening and prioritization in safety and efficacy evaluation, and risk assessment of drugs and chemicals. A database of 340 chemicals with percutaneous absorption was assembled. Two models were derived from the training set consisting 306 chemicals (90/10 random split). In addition to the experimental K(ow) values, over 300 2D and 3D atomic and molecular descriptors were analyzed using MDL's QsarIS computer program. Subsequently, the models were validated using both internal (leave-one-out) and external validation (test set) procedures. Using the stepwise regression analysis, three molecular descriptors were determined to have significant statistical correlation with K(p) (R2 = 0.8225): logK(ow), X0 (quantification of both molecular size and the degree of skeletal branching), and SsssCH (count of aromatic carbon groups). In conclusion, two models to estimate skin absorption were developed. When compared to other skin absorption QSAR models in the literature, our model incorporated more chemicals and explored a large number of descriptors. Additionally, our models are reasonably predictive and have met both internal and external statistical validations.

Correlation between structure, retention, property, and activity of biologically relevant 1,7-bis(aminoalkyl)diazachrysene derivatives.

PubMed

Šegan, Sandra; Trifković, Jelena; Verbić, Tatjana; Opsenica, Dejan; Zlatović, Mario; Burnett, James; Šolaja, Bogdan; Milojković-Opsenica, Dušanka

2013-01-01

The physicochemical properties, retention parameters (R(M)(0)), partition coefficients (logP(OW)), and pK(a) values for a series of thirteen 1,7-bis(aminoalkyl) diazachrysene (1,7-DAAC) derivatives were determined in order to reveal the characteristics responsible for their biological behavior. The investigated compounds inhibit three unrelated pathogens (the Botulinum neurotoxin serotype A light chain (BoNT/A LC), Plasmodium falciparum malaria, and Ebola filovirus) via three different mechanisms of action. To determine the most influential factors governing the retention and activities of the investigated diazachrysenes, R(M)(0), logP(OW), and biological activity values were correlated with 2D and 3D molecular descriptors, using a partial least squares regression. The resulting quantitative structure-retention (property) relationships indicate the importance of descriptors related to the hydrophobicity of the molecules (e.g., predicted partition coefficients and hydrophobic surface area). Quantitative structure-activity relationship models for describing biological activity against the BoNT/A LC and malarial strains also include overall compound polarity, electron density distribution, and proton donor/acceptor potential. Furthermore, models for Ebola filovirus inhibition are presented qualitatively to provide insights into parameters that may contribute to the compounds' antiviral activities. Overall, the models form the basis for selecting structural features that significantly affect the compound's absorption, distribution, metabolism, excretion, and toxicity profiles. Copyright © 2012 Elsevier B.V. All rights reserved.

Adsorption of organic stormwater pollutants onto activated carbon from sewage sludge.

PubMed

Björklund, Karin; Li, Loretta Y

2017-07-15

Adsorption filters have the potential to retain suspended pollutants physically, as well as attracting and chemically attaching dissolved compounds onto the adsorbent. This study investigated the adsorption of eight hydrophobic organic compounds (HOCs) frequently detected in stormwater - including four polycyclic aromatic hydrocarbons (PAHs), two phthalates and two alkylphenols - onto activated carbon produced from domestic sewage sludge. Adsorption was studied using batch tests. Kinetic studies indicated that bulk adsorption of HOCs occurred within 10 min. Sludge-based activated carbon (SBAC) was as efficient as tested commercial carbons for adsorbing HOCs; adsorption capacities ranged from 70 to 2800 μg/g (C initial  = 10-300 μg/L; 15 mg SBAC in 150 mL solution; 24 h contact time) for each HOC. In the batch tests, the adsorption capacity was generally negatively correlated to the compounds' hydrophobicity (log K ow ) and positively associated with decreasing molecule size, suggesting that molecular sieving limited adsorption. However, in repeated adsorption tests, where competition between HOCs was more likely to occur, adsorbed pollutant loads exhibited strong positive correlation with log K ow . Sewage sludge as a carbon source for activated carbon has great potential as a sustainable alternative for sludge waste management practices and production of a high-capacity adsorption material. Copyright © 2017 Elsevier Ltd. All rights reserved.

Demonstration of a consensus approach for the calculation of physicochemical properties required for environmental fate assessments

EPA Science Inventory

Eight software applications are compared for their performance in estimating the octanol-water partition coefficient (Kow), melting point, vapor pressure and water solubility for a dataset of polychlorinated biphenyls, polybrominated diphenyl ethers, polychlorinated dibenzodioxin...

Assessment and improvement of biotransfer models to cow's milk and beef used in exposure assessment tools for organic pollutants.

PubMed

Takaki, Koki; Wade, Andrew J; Collins, Chris D

2015-11-01

The aim of this study was to assess and improve the accuracy of biotransfer models for the organic pollutants (PCBs, PCDD/Fs, PBDEs, PFCAs, and pesticides) into cow's milk and beef used in human exposure assessment. Metabolic rate in cattle is known as a key parameter for this biotransfer, however few experimental data and no simulation methods are currently available. In this research, metabolic rate was estimated using existing QSAR biodegradation models of microorganisms (BioWIN) and fish (EPI-HL and IFS-HL). This simulated metabolic rate was then incorporated into the mechanistic cattle biotransfer models (RAIDAR, ACC-HUMAN, OMEGA, and CKow). The goodness of fit tests showed that RAIDAR, ACC-HUMAN, OMEGA model performances were significantly improved using either of the QSARs when comparing the new model outputs to observed data. The CKow model is the only one that separates the processes in the gut and liver. This model showed the lowest residual error of all the models tested when the BioWIN model was used to represent the ruminant metabolic process in the gut and the two fish QSARs were used to represent the metabolic process in the liver. Our testing included EUSES and CalTOX which are KOW-regression models that are widely used in regulatory assessment. New regressions based on the simulated rate of the two metabolic processes are also proposed as an alternative to KOW-regression models for a screening risk assessment. The modified CKow model is more physiologically realistic, but has equivalent usability to existing KOW-regression models for estimating cattle biotransfer of organic pollutants. Copyright © 2015. Published by Elsevier Ltd.

CKow -- A More Transparent and Reliable Model for Chemical Transfer to Meat and Milk

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

Rosenbaum, Ralph K.; McKone, Thomas E.; Jolliet, Olivier

The objective of this study is to increase the understanding and transparency of chemical biotransfer modeling into meat and milk and explicitly confront the uncertainties in exposure assessments of chemicals that require such estimates. In cumulative exposure assessments that include food pathways, much of the overall uncertainty is attributable to the estimation of transfer into biota and through food webs. Currently, the most commonly used meat and milk-biotransfer models date back two decades and, in spite of their widespread use in multimedia exposure models few attempts have been made to advance or improve the outdated and highly uncertain Kow regressionsmore » used in these models. Furthermore, in the range of Kow where meat and milk become the dominant human exposure pathways, these models often provide unrealistic rates and do not reflect properly the transfer dynamics. To address these issues, we developed a dynamic three-compartment cow model (called CKow), distinguishing lactating and non-lactating cows. For chemicals without available overall removal rates in the cow, a correlation is derived from measured values reported in the literature to predict this parameter from Kow. Results on carry over rates (COR) and biotransfer factors (BTF) demonstrate that a steady-state ratio between animal intake and meat concentrations is almost never reached. For meat, empirical data collected on short term experiments need to be adjusted to provide estimates of average longer term behaviors. The performance of the new model in matching measurements is improved relative to existing models--thus reducing uncertainty. The CKow model is straight forward to apply at steady state for milk and dynamically for realistic exposure durations for meat COR.« less

Critical body residues linked to octanol-water partitioning, organism composition, and LC50 QSARs: meta-analysis and model.

PubMed

Hendriks, A Jan; Traas, Theo P; Huijbregts, Mark A J

2005-05-01

To protect thousands of species from thousands of chemicals released in the environment, various risk assessment tools have been developed. Here, we link quantitative structure-activity relationships (QSARs) for response concentrations in water (LC50) to critical concentrations in organisms (C50) by a model for accumulation in lipid or non-lipid phases versus water Kpw. The model indicates that affinity for neutral body components such as storage fat yields steep Kpw-Kow relationships, whereas slopes for accumulation in polar phases such as proteins are gentle. This pattern is confirmed by LC50 QSARs for different modes of action, such as neutral versus polar narcotics and organochlorine versus organophosphor insecticides. LC50 QSARs were all between 0.00002 and 0.2Kow(-1). After calibrating the model with the intercepts and, for the first time also, with the slopes of the LC50 QSARs, critical concentrations in organisms C50 are calculated and compared to an independent validation data set. About 60% of the variability in lethal body burdens C50 is explained by the model. Explanations for differences between estimated and measured levels for 11 modes of action are discussed. In particular, relationships between the critical concentrations in organisms C50 and chemical (Kow) or species (lipid content) characteristics are specified and tested. The analysis combines different models proposed before and provides a substantial extension of the data set in comparison to previous work. Moreover, the concept is applied to species (e.g., plants, lean animals) and substances (e.g., specific modes of action) that were scarcely studied quantitatively so far.

Assessment of PDMS-water partition coefficients: implications for passive environmental sampling of hydrophobic organic compounds

USGS Publications Warehouse

DiFilippo, Erica L.; Eganhouse, Robert P.

2010-01-01

Solid-phase microextraction (SPME) has shown potential as an in situ passive-sampling technique in aquatic environments. The reliability of this method depends upon accurate determination of the partition coefficient between the fiber coating and water (Kf). For some hydrophobic organic compounds (HOCs), Kf values spanning 4 orders of magnitude have been reported for polydimethylsiloxane (PDMS) and water. However, 24% of the published data examined in this review did not pass the criterion for negligible depletion, resulting in questionable Kf values. The range in reported Kf is reduced to just over 2 orders of magnitude for some polychlorinated biphenyls (PCBs) when these questionable values are removed. Other factors that could account for the range in reported Kf, such as fiber-coating thickness and fiber manufacturer, were evaluated and found to be insignificant. In addition to accurate measurement of Kf, an understanding of the impact of environmental variables, such as temperature and ionic strength, on partitioning is essential for application of laboratory-measured Kf values to field samples. To date, few studies have measured Kf for HOCs at conditions other than at 20 degrees or 25 degrees C in distilled water. The available data indicate measurable variations in Kf at different temperatures and different ionic strengths. Therefore, if the appropriate environmental variables are not taken into account, significant error will be introduced into calculated aqueous concentrations using this passive sampling technique. A multiparameter linear solvation energy relationship (LSER) was developed to estimate log Kf in distilled water at 25 degrees C based on published physicochemical parameters. This method provided a good correlation (R2 = 0.94) between measured and predicted log Kf values for several compound classes. Thus, an LSER approach may offer a reliable means of predicting log Kf for HOCs whose experimental log Kf values are presently unavailable. Future research should focus on understanding the impact of environmental variables on Kf. Obtaining the data needed for an LSER approach to estimate Kf for all environmentally relevant HOCs would be beneficial to the application of SPME as a passive-sampling technique.

Quasi-equilibrium analysis of the ion-pair mediated membrane transport of low-permeability drugs.

PubMed

Miller, Jonathan M; Dahan, Arik; Gupta, Deepak; Varghese, Sheeba; Amidon, Gordon L

2009-07-01

The aim of this research was to gain a mechanistic understanding of ion-pair mediated membrane transport of low-permeability drugs. Quasi-equilibrium mass transport analyses were developed to describe the ion-pair mediated octanol-buffer partitioning and hydrophobic membrane permeation of the model basic drug phenformin. Three lipophilic counterions were employed: p-toluenesulfonic acid, 2-naphthalenesulfonic acid, and 1-hydroxy-2-naphthoic acid (HNAP). Association constants and intrinsic octanol-buffer partition coefficients (Log P(AB)) of the ion-pairs were obtained by fitting a transport model to double reciprocal plots of apparent octanol-buffer distribution coefficients versus counterion concentration. All three counterions enhanced the lipophilicity of phenformin, with HNAP providing the greatest increase in Log P(AB), 3.7 units over phenformin alone. HNAP also enhanced the apparent membrane permeability of phenformin, 27-fold in the PAMPA model, and 4.9-fold across Caco-2 cell monolayers. As predicted from a quasi-equilibrium analysis of ion-pair mediated membrane transport, an order of magnitude increase in phenformin flux was observed per log increase in counterion concentration, such that log-log plots of phenformin flux versus HNAP concentration gave linear relationships. These results provide increased understanding of the underlying mechanisms of ion-pair mediated membrane transport, emphasizing the potential of this approach to enable oral delivery of low-permeability drugs.

Relevance of octanol-water distribution measurements to the potential ecological uptake of multi-walled carbon nanotubes.

PubMed

Petersen, Elijah J; Huang, Qingguo; Weber, Walter J

2010-05-01

Many potential applications of carbon nanotubes (CNTs) require various physicochemical modifications prior to use, suggesting that nanotubes having varied properties may pose risks in ecosystems. A means for estimating bioaccumulation potentials of variously modified CNTs for incorporation in predictive fate models would be highly valuable. An approach commonly used for sparingly soluble organic contaminants, and previously suggested for use as well with carbonaceous nanomaterials, involves measurement of their octanol-water partitioning coefficient (KOW) values. To test the applicability of this approach, a methodology was developed to measure apparent octanol-water distribution behaviors for purified multi-walled carbon nanotubes and those acid treated. Substantial differences in apparent distribution coefficients between the two types of CNTs were observed, but these differences did not influence accumulation by either earthworms (Eisenia foetida) or oligochaetes (Lumbriculus variegatus), both of which showed minimal nanotube uptake for both types of nanotubes. The results suggest that traditional distribution behavior-based KOW approaches are likely not appropriate for predicting CNT bioaccumulation. Copyright (c) 2010 SETAC.

Persistent organic pollutants in Mediterranean seawater and processes affecting their accumulation in plankton.

PubMed

Berrojalbiz, Naiara; Dachs, Jordi; Del Vento, Sabino; Ojeda, María José; Valle, María Carmen; Castro-Jiménez, Javier; Mariani, Giulio; Wollgast, Jan; Hanke, Georg

2011-05-15

The Mediterranean and Black Seas are unique marine environments subject to important anthropogenic pressures due to riverine and atmospheric inputs of organic pollutants. Here, we report the results obtained during two east-west sampling cruises in June 2006 and May 2007 from Barcelona to Istanbul and Alexandria, respectively, where water and plankton samples were collected simultaneously. Both matrixes were analyzed for hexaclorochyclohexanes (HCHs), hexachlorobenzene (HCB), and 41 polychlorinated biphenyl (PCB) congeners. The comparison of the measured HCB and HCHs concentrations with previously reported dissolved phase concentrations suggests a temporal decline in their concentrations since the 1990s. On the contrary, PCB seawater concentrations did not exhibit such a decline, but show a significant spatial variability in dissolved concentrations with lower levels in the open Western and South Eastern Mediterranean, and higher concentrations in the Black, Marmara, and Aegean Seas and Sicilian Strait. PCB and OCPs (organochlorine pesticides) concentrations in plankton were higher at lower plankton biomass, but the intensity of this trend depended on the compound hydrophobicity (K(OW)). For the more persistent PCBs and HCB, the observed dependence of POP concentrations in plankton versus biomass can be explained by interactions between air-water exchange, particle settling, and/or bioaccumulation processes, whereas degradation processes occurring in the photic zone drive the trends shown by the more labile HCHs. The results presented here provide clear evidence of the important physical and biogeochemical controls on POP occurrence in the marine environment.

Treatability assessment of polycyclic aromatic hydrocarbons contaminated marine sediments using permanganate, persulfate and Fenton oxidation processes.

PubMed

Shih, Yu-Jen; Binh, Nguyen Thanh; Chen, Chiu-Wen; Chen, Chih-Feng; Dong, Cheng-Di

2016-05-01

Various chemical oxidation techniques, such as potassium permanganate (KMnO4), sodium persulfate (Na2S2O8), Fenton (H2O2/Fe(2+)), and the modified persulfate and Fenton reagents (activated by ferrous complexes), were carried out to treat marine sediments that were contaminated with polycyclic aromatic hydrocarbons (PAHs) and dredged from Kaohsiung Harbor in Taiwan. Experimental results revealed that KMnO4 was the most effective of the tested oxidants in PAH degradation. Owing to the high organic matter content in the sediment that reduced the efficiencies of Na2S2O8 and regular Fenton reactions, a large excess of oxidant was required. Nevertheless, KH2PO4, Na4P2O7 and four chelating agents (EDTA, sodium citrate, oxalic acid, and sodium oxalate) were utilized to stabilize Fe(II) in activating the Na2S2O8 and Fenton oxidations, while Fe(II)-citrate remarkably promoted the PAH degradation. Increasing the molecular weight and number of rings of PAH did not affect the overall removal efficiencies. The correlation between the effectiveness of the oxidation processes and the physicochemical properties of individual PAH was statistically analyzed. The data implied that the reactivity of PAH (electron affinity and ionization potential) affected its treatability more than did its hydrophobicity (Kow, Koc and Sw), particularly using experimental conditions under which PAHs could be effectively oxidized. Copyright © 2016 Elsevier Ltd. All rights reserved.

Prediction of the Fate of Organic Compounds in the Environment From Their Molecular Properties: A Review

PubMed Central

Mamy, Laure; Patureau, Dominique; Barriuso, Enrique; Bedos, Carole; Bessac, Fabienne; Louchart, Xavier; Martin-laurent, Fabrice; Miege, Cecile; Benoit, Pierre

2015-01-01

A comprehensive review of quantitative structure-activity relationships (QSAR) allowing the prediction of the fate of organic compounds in the environment from their molecular properties was done. The considered processes were water dissolution, dissociation, volatilization, retention on soils and sediments (mainly adsorption and desorption), degradation (biotic and abiotic), and absorption by plants. A total of 790 equations involving 686 structural molecular descriptors are reported to estimate 90 environmental parameters related to these processes. A significant number of equations was found for dissociation process (pKa), water dissolution or hydrophobic behavior (especially through the KOW parameter), adsorption to soils and biodegradation. A lack of QSAR was observed to estimate desorption or potential of transfer to water. Among the 686 molecular descriptors, five were found to be dominant in the 790 collected equations and the most generic ones: four quantum-chemical descriptors, the energy of the highest occupied molecular orbital (EHOMO) and the energy of the lowest unoccupied molecular orbital (ELUMO), polarizability (α) and dipole moment (μ), and one constitutional descriptor, the molecular weight. Keeping in mind that the combination of descriptors belonging to different categories (constitutional, topological, quantum-chemical) led to improve QSAR performances, these descriptors should be considered for the development of new QSAR, for further predictions of environmental parameters. This review also allows finding of the relevant QSAR equations to predict the fate of a wide diversity of compounds in the environment. PMID:25866458

The Geochemical Behavior and Transport Characteristics of Xenoestrogens

NASA Astrophysics Data System (ADS)

Wallace, T. C.; Bennett, P. C.

2003-12-01

Xenoestrogens are estrogenic active synthetic chemicals that mimic the actions of female sex hormones. Xenoestrogens can be produced synthetically and naturally, and exposure can occur from a variety of sources- food additives, plastics, pesticides, or pharmaceuticals. These environmental chemicals are also known as endocrine disruptors because exposure to low doses (ng/L) have been linked to adverse effects in the reproductive and developmental stages in aquatic species (i.e. reproductive anomalies, feminization, infertility, alterations in growth during life cycles, and changes in community structures). Determining the exposure risks of these toxicological compounds, however, requires a better understanding of the geochemical behavior and transport of synthetic estrogens it is discharged to. Estrogen and its metabolites are also useful tracers because of their specific medical usage (sources from birth control pills, estrogen replacement therapy, and livestock farming), slow degradation before excretion, and unique physiochemical properties (low volatility, hydrophobicity, and high Kow). Estradiol concentrations analyzed by an enzyme-linked immunoassay (ELISA) show that <2-55 ng/L are discharged to Walnut Creek, a stream that also connects to the Colorado River(TX). The bioavailability of these compounds is affected by sorption processes, where xenoestrogens become associated with solid phases. A series of batch sorption experiments using sediment collected from Walnut Creek downstream of an Austin waste water treatment plant and synthetic estrogen standards (Simga@ Estrone, 17B-Estradiol, and Estriol), examined the distribution of estrogen between solid and aqueous phases. Analysis of the concentrations sorbed to sediment result in Freundlich sorption isotherms using HPLC/UV techniques (High Performance Liquid Chromatography with UV detectors- 220 and 280nm). Sorption occurs rapidly with 98% of 17B-Estradiol sorbed within 30 minutes (Estriol=80%, Estrone=95%), which is compared to photolysis degradation rates under UV and a broader spectrum sun lamp. Ultraviolet/Visible (UV/VIS) spectroscopy of the estrogen standards with dilute fulvic acid may indicate complexing with organic material. The hydrophobic nature of estrogen molecules due to a phenolic group seem to play a large role in the sorption rate. This sorption may alter direct photolysis decay rates, thereby acting as both a `sunscreen' and a carrier by increasing the exposure distance and bioavailability of xenoestrogens in the aquatic environment.

ESTIMATING DISSOLVED ORGANIC CARBON PARTITION COEFFICIENTS FOR NONIONIC ORGANIC CHEMICALS

EPA Science Inventory

A literature search was performed for dissolved organic carbon/water partition coefficients for nonionic chemicals (Kdoc) and Kdoc data was taken from more than sixty references. The Kdoc data were evaluated as a function of the n-octanol/water partition coefficients (Kow). A pre...

Progesterone binding nano-carriers based on hydrophobically modified hyperbranched polyglycerols

NASA Astrophysics Data System (ADS)

Alizadeh Noghani, M.; Brooks, D. E.

2016-02-01

Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models.Progesterone (Pro) is a potent neurosteroid and promotes recovery from moderate Traumatic Brain Injury but its clinical application is severely impeded by its poor water solubility. Here we demonstrate that reversibly binding Pro within hydrophobically modified hyperbranched polyglycerol (HPG-Cn-MPEG) enhances its solubility, stability and bioavailability. Synthesis, characterization and Pro loading into HPG-Cn-MPEG is described. The release kinetics are correlated with structural properties and the results of Differential Scanning Calorimetry studies of a family of HPG-Cn-MPEGs of varying molecular weight and alkylation. While the maximum amount of Pro bound correlates well with the amount of alkyl carbon per molecule contributing to its hydrophobicity, the dominant first order rate constant for Pro release correlates strongly with the amount of structured or bound water in the dendritic domain of the polymer. The results provide evidence to justify more detailed studies of interactions with biological systems, both single cells and in animal models. Electronic supplementary information (ESI) available: Fig. S-1: chemical structure of progesterone (Pro). Fig. S-2: 1H NMR spectrum of HPG-C8-MPEG. Fig. S-3: GPC chromatogram of HPG-C8-MPEG. Fig. S-4: 1H NMR spectrum of HPG-C12-MPEG. Fig. S-5: GPC chromatogram of HPG-C8-MPEG. Fig. S-6: FTIR spectrum of HPG-C8-MPEG. Fig. S-7: inverse-gated 13C NMR spectrum of HPG-C8-MPEG in methanol-d4. Fig. S-8: semi-log plot to determine initial rapid release kinetics for HPG-C8-MPEG/Pro in PBS. Fig. S-9: semi-log plot to determine secondary slow release kinetics for HPG-C8-MPEG/Pro in PBS. Fig. S-10: semi-log plot illustrating the kinetics of Pro release from HPG-C8-MPEG/Pro in plasma. Fig. S-11: dependence of k1 and Vp - Va. Fig. S-12: correlation between the maximum binding capacity of HPG-Cn-MPEG polymeric systems for binding Pro and their total mass of alkyl carbon external to the oxygen (R2 = 0.77 and p < 0.025). Table S-1: effect of loaded Pro on HPG-Cn-MPEG size. Fig. S-13. DLS size determination of HPG-C10-MPEG at 2 mg ml-1 (on the left) and HPG-C10-MPEG/Pro at 2 mg ml-1 of polymer and 25 μg ml-1 of Pro (on the right). The minor population of larger particles was reduced in diameter by Pro binding, illustrated above, consistent with an earlier report.11 See DOI: 10.1039/c5nr08175k

Solubilization of polycyclic aromatic hydrocarbons in micellar nonionic surfactant solutions

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

Edwards, D.A.; Luthy, R.G.; Liu, Zhongbao

1991-01-01

Experimental data are presented on the enhanced apparent solubilities of naphthalene, phenanthrene, and pyrene resulting from solubilization in aqueous solutions of four commercial, nonionic surfactants: an alkyl polyoxyethylene (POE) type, two octylphenol POE types, and a nonylphenol POE type. Apparent solubilities of the polycyclic aromatic hydrocarbon (PAH) compounds in surfactant solutions were determined by radiolabeled techniques. Solubilization of each PAH compound commenced at the surfactant critical micelle concentration and was proportional to the concentration of surfactant in micelle form. The partitioning of organic compounds between surfactant micelles and aqueous solution is characterized by a mole fraction micelle-phase/aqueous-phase partition coefficient, K{submore » m}. Values of log K{sub m} for PAH compounds in surfactant solutions of this study range from 4.57 to 6.53. Log K{sub m} appears to be a linear function of log K{sub ow} for a given surfactant solution. A knowledge of partitioning in aqueous surfactant systems is a prerequisite to understanding mechanisms affecting the behavior of hydrophobic organic compounds in soil-water systems in which surfactants play a role in contaminant remediation or facilitated transport.« less

Antioxidant activity of gallic acid and methyl gallate in triacylglycerols of Kilka fish oil and its oil-in-water emulsion.

PubMed

Asnaashari, Maryam; Farhoosh, Reza; Sharif, Ali

2014-09-15

The anti-DPPH radical effect as well as anti-peroxide activity of gallic acid, methyl gallate, and α-tocopherol in a bulk Kilka fish oil and its oil-in-water emulsion stabilized by soy protein isolate at 55°C were investigated. Gallic acid with the lowest hydrophobicity (log P=-0.28) was found to be the most active antiradical agent (IC50=29.5 μM), followed by methyl gallate (IC50=38.0 μM, log P=-0.23) and α-tocopherol (IC50=105.3 μM, log P=0.70). The anti-peroxide activity in the bulk oil system decreased in the order of methyl gallate>gallic acid>α-tocopherol. In the emulsion system, methyl gallate still behaved better than gallic acid, but the highest activity belonged to α-tocopherol. Based on the calculation of a number of kinetic parameters, the antioxidants, in general, showed better performances in the bulk oil system than in the emulsion system. Copyright © 2014 Elsevier Ltd. All rights reserved.

TRAVIS AND ARMS REVISITED: A SECOND LOOK AT A WIDELY USED BIOCONCENTRATION ALGORITHM

EPA Science Inventory

In 1988, Travis and Arms reviewed the literature and collected data to develop a relationship between the octanolwater partition coefficient (Kow) and the uptake of organic compounds into milk and beef (Travis and Arms, 1988). These equations have been utilized for predicting bio...

A novel prediction approach for antimalarial activities of Trimethoprim, Pyrimethamine, and Cycloguanil analogues using extremely randomized trees.

PubMed

Nattee, Cholwich; Khamsemanan, Nirattaya; Lawtrakul, Luckhana; Toochinda, Pisanu; Hannongbua, Supa

2017-01-01

Malaria is still one of the most serious diseases in tropical regions. This is due in part to the high resistance against available drugs for the inhibition of parasites, Plasmodium, the cause of the disease. New potent compounds with high clinical utility are urgently needed. In this work, we created a novel model using a regression tree to study structure-activity relationships and predict the inhibition constant, K i of three different antimalarial analogues (Trimethoprim, Pyrimethamine, and Cycloguanil) based on their molecular descriptors. To the best of our knowledge, this work is the first attempt to study the structure-activity relationships of all three analogues combined. The most relevant descriptors and appropriate parameters of the regression tree are harvested using extremely randomized trees. These descriptors are water accessible surface area, Log of the aqueous solubility, total hydrophobic van der Waals surface area, and molecular refractivity. Out of all possible combinations of these selected parameters and descriptors, the tree with the strongest coefficient of determination is selected to be our prediction model. Predicted K i values from the proposed model show a strong coefficient of determination, R 2 =0.996, to experimental K i values. From the structure of the regression tree, compounds with high accessible surface area of all hydrophobic atoms (ASA_H) and low aqueous solubility of inhibitors (Log S) generally possess low K i values. Our prediction model can also be utilized as a screening test for new antimalarial drug compounds which may reduce the time and expenses for new drug development. New compounds with high predicted K i should be excluded from further drug development. It is also our inference that a threshold of ASA_H greater than 575.80 and Log S less than or equal to -4.36 is a sufficient condition for a new compound to possess a low K i . Copyright © 2016 Elsevier Inc. All rights reserved.

Retention equations of nonionic organic chemicals in soil column chromatography with methanol-water eluents.

PubMed

Xu, Feng; Liang, Xinmiao; Lin, Bingcheng

2002-01-01

Research efforts dealing with chemical transportation in soils are needed to prevent damage to ground water. Methanol-containing solvents can increase the translocation of nonionic organic chemicals (NOCs). In this study, a general log-linear retention equation, log k' = log k'w - Sphi (Eq. [1]), was developed to describe the mobilities of NOCs in soil column chromatography (SCC). The term phi denotes the volume fraction of methanol in eluent, k' is the capacity factor of a solute at a certain phi value, and log k'w and -S are the intercept and slope of the log k' vs. phi plot. Two reference soils (GSE 17204 and GSE 17205) were used as packing materials, and were eluted by isocratic methanol-water mixtures. A model of linear solvation energy relationships (LSER) was applied to analyze the k' from molecular interactions. The most important factor determining the transportation was found to be the solute hydrophobic partition in soils, and the second-most important factor was the solute hydrogen-bond basicity (hydrogen-bond accepting ability), while the less important factor was the solute dipolarity-polarizability. The solute hydrogen-bond acidity (hydrogen-bond donating ability) was statistically unimportant and deletable. From the LSER model, one could also obtain Eq. [1]. The experimental k' data of 121 NOCs can be accurately explained by Eq. [1]. The equation is promising to estimate the solute mobility in pure water by extrapolating from lower-capacity factors obtained in methanol-water mixed eluents.

Biochemical Traits, Survival and Biological Properties of the Probiotic Lactobacillus plantarum Grown in the Presence of Prebiotic Inulin and Pectin as Energy Source

PubMed Central

Nazzaro, Filomena; Fratianni, Florinda; Orlando, Pierangelo; Coppola, Raffaele

2012-01-01

The viability of the probiotic strain Lactobacillus plantarum subsp. plantarum, after its passage through simulated gastric and pancreatic juices, was evaluated as function of its pre-growth in a medium containing the known prebiotics pectin or inulin, and was compared to glucose used as control. The presence of pectin or inulin did not markedly affect the growth (10.07 log10 colony forming units/mL and 10.28 log10 colony forming units/mL for pectin and inulin respectively versus 10.42 log10 colony forming units/mL obtained for glucose). Pectin and inulin, in contrast to glucose, induced cell stress resistance against gastrointestinal juices (Δ log101.5 and 2.4 colony forming units/mL respectively, versus Δ log10 4.0 for glucose). The data were corroborated by the analysis of the protein pattern following stress treatments which, in the case of microbial cells grown with glucose, revealed a more marked protein degradation after the double passage through simulated gastric and intestinal juices. Inulin stimulated the production of the relevant healthy bio-molecule butyrate, which amount was 30% higher respect of growth in the presence of glucose. Inulin and pectin improved cell DPPH scavenging activity, and an impressive hydrophobicity (35.28% and 34.81%, respectively) was observed with respect to the microbial growth in presence of glucose (3.39%). PMID:24281559

Polymer Stabilized Nanosuspensions Formed via Flash Nanoprecipitation: Nanoparticle Formation, Formulation, and Stability

NASA Astrophysics Data System (ADS)

Zhu, ZhengXi

Nanoparticles loaded with hydrophobic components (e.g., active pharmaceutical ingredients, medical diagnostic agents, nutritional or personal care chemicals, catalysts, dyes/pigments, and substances with exceptional magnetic/optical/electronic/thermal properties) have tremendous industrial applications. The common desire is to efficiently generate nanoparticles with a desired size, size distribution, and size stability. Recently, Flash NanoPrecipition (FNP) technique with a fast, continuous, and easily scalable process has been developed to efficiently generate hydrophobe-loaded nanoparticles. This dissertation extended this technique, optimized process conditions and material formulations, and gave new insights into the mechanism and kinetics of nanoparticle formation. This dissertation demonstrated successful generation of spherical beta-carotene nanoparticles with an average diameter of 50--100 nm (90 wt% nanoparticles below 200 nm), good size stability (maintained an average diameter below 200 nm for at least one week in saline), and much higher loading (80--90 wt%) than traditional carriers, such as micelles and polymersomes (typically <20 wt%). Moreover, the nanoparticles are amorphous and expected to have a high dissolution rate and bioavailability. To give insights into the mechanism and kinetics of nanoparticle formation, much remarkable evidence supported the kinetically frozen structures of the nanoparticles rather than the thermodynamic equilibrium micelles. Time scales of the particle formation via FNP were proposed. To optimize the material formulations, either polyelectrolytes (i.e., epsilon-polylysine, branched and linear poly(ethylene imine), and chitosan) or amphiphilic diblock copolymers (i.e., polystyrene-b-poly(ethylene glycol) (PS-b-PEG), polycarprolactone-b-poly(ethylene glycol) (PCL-b-PEG), poly(lactic acid)-b-poly(ethylene glycol) (PLA-b-PEG), and poly(lactic-co-glycolic acid)-b-poly(ethylene glycol) (PLGA-b-PEG)) were selectively screened to study the nanoparticle size, distribution, and stability. The effect of the molecular weight of the polymers and pH were also studied. Chitosan and PLGA-b-PEG best stabilized the beta-carotene nanoparticles. Solubility of the hydrophobic drug solute in the aqueous mixture was considered to dominate the nanoparticle stability (i.e., size and morphology) in terms of Ostwald ripening and recrystallization. The lower solubility the drug is of, the greater stability the nanoparticles have. Chemically bonding drug compounds with cleavable hydrophobic moieties to form prodrugs were used to enhance their hydrophobicity and thus the nanoparticle stability. It opened a generic strategy to enhance the stability of nanoparticles formed via FNP. beta-carotene, paclitaxel, paclitaxel prodrug, betulin, hydrocortisone, and hydrocortisone prodrug as the drugs were studied. Solubility parameter (delta), and octanol/water partition coefficients (LogP), provide hydrophobicity indicators for the compounds. LogP showed a good correlation with the nanoparticle stability. An empirical rule was built to conveniently predict particle stability for randomly selected drugs. To optimize the process conditions, two-stream confined impinging jet mixer (CIJ) and four-stream confined vortex jet mixer were used. The particle size was studied by varying drug and polymer concentrations, and flow rate (corresponding to Reynolds number (Re)). To extend the FNP technique, this dissertation demonstrated successful creation of stabilized nanoparticles by integrating an in-situ reactive coupling of a hydrophilic polymer block with a hydrophobic one with FNP. The kinetics of the fast coupling reaction was studied. This dissertation also introduced polyelectrolytes (i.e., epsilon-polylysine, poly(ethylene imine), and chitosan) into FNP to electrosterically stabilize nanoparticles.

LAS bioconcentration is isomer specific

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

Tolls, J.; Haller, M.; Graaf, I. de

1995-12-31

The authors measured parent compound specific bioconcentration data for linear alkylbenzene sulfonates in Pimephales promelas. They did so by using cold, custom synthesized sulfophenyl alkanes. They observed that, within homologous series of isomers, the uptake rate constants (k{sub 1}) and the bioconcentration factor (BCF) increase with increasing number of carbon atoms in the alkyl chain (n{sub C-atoms}). In contrast, the elimination rate constant k{sub 2} appears to be independent of the alkyl chain length. Regressions of log BCF vs n{sub C-atoms} yielded different slopes for the homologous groups of the 5- and the 2-sulfophenyl alkane isomers. Regression of all logmore » BCF-data vs log 1/CMC yielded a good description of the data. However, when regressing the data for both homologous series separately again very different slopes are obtained. The results therefore indicate that hydrophobicity-bioconcentration relationships may be different for different homologous groups of sulfophenyl alkanes.« less

The influence of vertical sorbed phase transport on the fate of organic chemicals in surface soils.

PubMed

McLachlan, Michael S; Czub, Gertje; Wania, Frank

2002-11-15

Gaseous exchange between surface soil and the atmosphere is an important process in the environmental fate of many chemicals. It was hypothesized that this process is influenced by vertical transport of chemicals sorbed to soil particles. Vertical sorbed phase transport in surface soils occurs by many processes such as bioturbation, cryoturbation, and erosion into cracks formed by soil drying. The solution of the advection/diffusion equation proposed by Jury et al. to describe organic chemical fate in a uniformly contaminated surface soil was modified to include vertical sorbed phase transport This process was modeled using a sorbed phase diffusion coefficient, the value of which was derived from soil carbon mass balances in the literature. The effective diffusivity of the chemical in a typical soil was greater in the modified model than in the model without sorbed phase transport for compounds with log K(OW) > 2 and log K(OA) > 6. Within this chemical partitioning space, the rate of volatilization from the surface soil was larger in the modified model than in the original model by up to a factor of 65. The volatilization rate was insensitive to the value of the sorbed phase diffusion coefficient throughout much of this chemical partitioning space, indicating that the surface soil layer was essentially well-mixed and that the mass transfer coefficient was determined by diffusion through the atmospheric boundary layer only. When this process was included in a non-steady-state regional multimedia chemical fate model running with a generic emissions scenario to air, the predicted soil concentrations increased by upto a factor of 25,whilethe air concentrations decreased by as much as a factor of approximately 3. Vertical sorbed phase transport in the soil thus has a major impact on predicted air and soil concentrations, the state of equilibrium, and the direction and magnitude of the chemical flux between air and soil. It is a key process influencing the environmental fate of persistent organic pollutants (POPs).

Characterize Behaviour of Emerging Pollutants in Artificial Recharge: Column Experiments - Experiment Design and Results of Preliminary Tests

NASA Astrophysics Data System (ADS)

Wang, H.; Carrera, J.; Ayora, C.; Licha, T.

2012-04-01

Emerging pollutants (EPs) have been detected in water resources as a result of human activities in recent years. They include pharmaceuticals, personal care products, dioxins, flame retardants, etc. They are a source of concern because many of them are resistant to conventional water treatment, and they are harmful to human health, even in low concentrations. Generally, this study aims to characterize the behaviour of emerging pollutants in reclaimed water in column experiments which simulates artificial recharge. One column set includes three parts: influent, reactive layer column (RLC) and aquifer column (AC). The main influent is decided to be Secondary Effluent (SE) of El Prat Wastewater Treatment Plant, Barcelona. The flow rate of the column experiment is 0.9-1.5 mL/min. the residence time of RLC is designed to be about 1 day and 30-40 days for AC. Both columns are made of stainless steel. Reactive layer column (DI 10cm * L55cm) is named after the filling material which is a mixture of organic substrate, clay and goethite. One purpose of the application of the mixture is to increase dissolve organic carbon (DOC). Leaching test in batchs and columns has been done to select proper organic substrate. As a result, compost was selected due to its long lasting of releasing organic matter (OM). The other purpose of the application of the mixture is to enhance adsorption of EPs. Partition coefficients (Kow) of EPs indicate the ability of adsorption to OM. EPs with logKow>2 could be adsorbed to OM, like Ibuprofen, Bezafibrate and Diclofenac. Moreover, some of EPs are charged in the solution with pH=7, according to its acid dissociation constant (Ka). Positively charged EPs, for example Atenolol, could adsorb to clay. In the opposite, negatively charged EPs, for example Gemfibrozil, could adsorb to goethite. Aquifer column (DI 35cm * L1.5m) is to simulate the processes taking place in aquifer in artificial recharge. The filling of AC has two parts: silica sand and compost. The grain size of the sand is about 0.5mm. Aquifer deposits usually contain some natural organic matter. Therefore, compost (<1mm) was selected to be mixed with sand with the ratio of 1:99. Long residence time of AC and high concentration of DOC are favourable to generate variable redox states, which favour EPs degradation.

Comparison of toxicity of class-based organic chemicals to algae and fish based on discrimination of excess toxicity from baseline level.

PubMed

Li, Jin J; Tai, Hong W; Yu, Yang; Wen, Yang; Wang, Xiao H; Zhao, Yuan H

2015-07-01

Toxicity data to fish and algae were used to investigate excess toxicity between species. Results show that chemicals exhibiting excess toxicity to fish also show excess toxicity to algae for most of the compounds. This indicates that they share the same mode of action between species. Similar relationships between logKOW and toxicities to fish and algae for baseline and less inert compounds suggest that they have similar critical body residues in the two species. Differences in excess toxicity for some compounds suggest that there is a difference of physiological structure and metabolism between fish and algae. Some reactive compounds (e.g. polyamines) exhibit greater toxic effects for algae than those for fish because of relatively low bio-uptake potential of these hydrophilic compounds in fish as compared with that in algae. Esters exhibiting greater toxicity in fish than that in algae indicate that metabolism can affect the discrimination of excess toxicity from baseline level. Algae growth inhibition is a very good surrogate for fish lethality. This is not only because overall toxicity sensitivity to algae is greater than that to fish, but also the excess toxicity calculated from algal toxicity can better reflect reactivity of compounds with target molecules than fish toxicity. Copyright © 2015 Elsevier B.V. All rights reserved.

Uptake and release of polar compounds in SDB-RPS Empore disks; implications for their use as passive samplers.

PubMed

Shaw, Melanie; Eaglesham, Geoff; Mueller, Jochen F

2009-03-01

Demand for sensitive monitoring tools to detect trace levels of pollutants in aquatic environments has led to investigation of sorbents to complement the suite of passive sampling phases currently in use. Styrenedivinylbenzene-reverse phase sulfonated (SDB-RPS) sorbents have a high affinity for polar organic compounds such as herbicides. However, the applicability of the performance reference compound (PRC) concept as an in situ calibration method for passive samplers that use this or similar sampling phases has yet to be validated. In this study, laboratory based calibration experiments were conducted to compare the uptake kinetics of several key pesticides with the release of three pre-loaded PRCs in Chemcatchers using SDB-RPS Empore disks deployed with a membrane and without (naked). For compounds with log K(OW) values ranging from 1.8 to 4.0, uptake into samplers with a membrane and without was linear over 30d and 10d, respectively. While uptake was linear and reproducible, PRC loss was not linear, meaning that the dissipation rates of these PRCs cannot be used to estimate field exposure conditions on uptake rates. An alternative in situ calibration technique using PRC loaded polydimethylsiloxane (PDMS) disks deployed alongside the Empore disk samplers as a surrogate calibration phase has been tested in the current study and shows promise for future applications.

Bilastine: an environmental risk assessment.

PubMed

Lucero, María Luisa; Peither, Armin; Ledo, Francisco

2015-10-01

Bilastine is a new oral selective, non-sedating histamine H1 antagonist for the symptomatic treatment of allergic rhinoconjunctivitis and urticaria. The European Medicines Agency requires an Environmental Risk Assessment (ERA) for all novel medicines for human use. To calculate the bilastine predicted environmental concentration in surface water (PECsw; phase I ERA), and to determine the effects of bilastine on aquatic systems (phase II [tier A]). Bilastine PECsw was calculated using the maximum daily dosage (20 mg), assuming that all administered bilastine was released into the aquatic environment. A persistence, bioaccumulation and toxicity assessment was conducted using the log Kow from the molecular structure. In phase II (tier A), a ready biodegradability test was performed, and bilastine's potential toxicity to various aquatic and sediment-dwelling micro-organisms was evaluated. Bilastine PECSW was calculated as 0.1 μg L(-1), and the compound was not readily biodegradable. Bilastine had no significant effects on Chironomus riparius midges, or on the respiration rate of activated sludge. For green algae, the bilastine no observed effect concentration (NOEC) was 22 mg L(-1); bilastine had no effect on zebra fish development, or on the reproduction rate of daphnids. Bilastine NOEC values against zebra fish, algae, daphnids, and aerobic organisms in activated sludge were at least 130 000-fold greater than the calculated PECSW value. No environmental concerns exist from bilastine use in patients with allergic rhinoconjunctivitis or urticaria.

Removal of naproxen and bezafibrate by activated sludge under aerobic conditions: kinetics and effect of substrates.

PubMed

Tang, Ying; Li, Xiao-Ming; Xu, Zhen-Cheng; Guo, Qing-Wei; Hong, Cheng-Yang; Bing, Yong-Xin

2014-01-01

Naproxen and bezafibrate fall into the category of pharmaceuticals that have been widely detected in the aquatic environment, and one of the major sources is the effluent discharge from wastewater treatment plants. This study investigated the sorption and degradation kinetics of naproxen and bezafibrate in the presence of activated sludge under aerobic conditions. Experimental results indicated that the adsorption of pharmaceuticals by activated sludge was rapid, and the relative adsorbabilities of the two-target compounds were based on their log Kow and pKa values. The adsorption data could be well interpreted by the pseudo-second-order kinetic model. The degradation process could be described by the pseudo-first-order kinetic model, whereas the pseudo-second-order kinetics were also well suited to describe the degradation process of the selected compounds at low concentrations. Bezafibrate was more easily degraded by activated sludge compared with naproxen. The spiked concentration of the two-target compounds was negatively correlated with k1 and k2s , indicating that the substrate inhibition effect occurred at the range of studied concentrations. Chemical oxygen demand (COD) did not associate with naproxen degradation; thus, COD is not an alternative method that could be applied to investigate natural organic matter's impact on degradation of pharmaceuticals by activated sludge. © 2013 International Union of Biochemistry and Molecular Biology, Inc.

A Systematic Evaluation of Analogs for the Read-across ...

EPA Pesticide Factsheets

Read-across is a data gap filling technique widely used within category and analog approaches to predict a biological property for a target data-poor chemical using known information from similar (source analog) chemical(s). Potential source analogs are typically identified based on structural similarity. Although much guidance has been published for read-across, practical guiding principles for the identification and evaluation of the scientific validity of source analogs, which is a critical step in deriving a robust read-across prediction, remains largely lacking.This case study explores the extent to which 3 structure descriptor sets (Pubchem, Chemotyper and MoSS) and their combinations are able to identify valid analogs for reading across Estrogen Receptor (ER) activity for a specific class of chemicals: hindered phenols. For each target chemical, two sets of analogs (hindered and non-hindered phenols) were selected using each descriptor set with two cut-offs: (1). Minimum Tanimoto similarity (range 0.1 - 0.9), and (2). Closest N analogs (range 1 - 10). Each target-analog pair was then evaluated for its agreement with measured ER binding and agonism. Subsequently, the analogs were filtered using physchem properties (LogKow & Molecular Volume) and the resultant agreement between each target-analog pair was evaluated. The data set comprised 462 hindered phenols and 296 non-hindered phenols. The results demonstrate that: (1). The concordance in ER activity r

A Systematic Evaluation of Analogs and Automated Read ...

EPA Pesticide Factsheets

Read-across is a data gap filling technique widely used within category and analog approaches to predict a biological property for a data-poor (target) chemical using known information from similar (source analog) chemical(s). Potential source analogs are typically identified based on structural similarity. Although much guidance has been published for read-across, practical principles for the identification and evaluation of the scientific validity of source analogs remains lacking. This case study explores how well 3 structure descriptor sets (Pubchem, Chemotyper and MoSS) are able to identify analogs for read-across and predict Estrogen Receptor (ER) binding activity for a specific class of chemicals: hindered phenols. For each target chemical, analogs were selected using each descriptor set with two cut-offs: (1) Minimum Tanimoto similarity (range 0.1 - 0.9), and (2) Closest N analogs (range 1 - 10). Each target-analog pair was then evaluated for its agreement with measured ER binding and agonism. The analogs were subsequently filtered using: (1) physchem properties (LogKow & Molecular Volume), and (2) number of literature sources as a marker for the quality of the experimental data. A majority vote prediction was made for each target phenol by reading-across from the closest N analogs. The data set comprised 462 hindered phenols and 257 non-hindered phenols. The results demonstrate that: (1) The concordance in ER activity rises with increasing similarity,

Integrating Monitoring and Genetic Methods To Infer Historical ...

EPA Pesticide Factsheets

Common and roseate terns are migratory piscivorous seabirds with major breeding colonies within feeding range of thepolychlorinated biphenyl (PCB)-contaminated New Bedford Harbor (NBH, MA, USA) Superfund site. Our longitudinal study shows that before PCB discharges into NBH ceased (late 1970s), tern eggs had very high but variable PCB concentrations. However, egg concentrations of PCBs as well as DDE (1,1-bis(p-chlorophenyl)-2,2-dichloroethene), the degradation product of the ubiquitous global contaminant DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane), have since declined. Rate constants for temporal decline of PCB congeners in tern eggs varied inversely with log10KOW (n-octanol−water partition coefficient), shifting egg congener patterns away from those characterizing NBH sediment. To estimate the toxic effects on tern eggs of PCB dioxin-like congener (DLC) exposures, we extrapolated published laboratory data on common terns to roseate terns by characterizing genetic and functional similarities in species aryl hydrocarbon receptors (AHRs), which mediate DLC sensitivity. Our assessment of contaminant risks suggests that terns breeding near NBH were exposed historically to toxic levels of PCBs and DDE; however, acute effects on tern egg development have become less likely since the 1970s. Our approach demonstrates how comparative genetics at target loci can effectively increase the range of inference for chemical risk assessments from tested to untested a

U.S. EPA, Pesticide Product Label, ROCKLAND KLEEN-KOW CONCENTRATE DAIRY & LIVESTOCK SPRAY CONT. CIODRIN &, 12/17/1968

EPA Pesticide Factsheets

2011-04-14

... "~-' ;c-+:cns 1 .... ._""- .. u,-_ u~c ~ack~~Lbers or ~ace ru~~e~~ ~ce ~l;es, ~'lX 1 :uart "~r 4 ~a!lQ~s . ) .". trJt1on. :_1~:; ~a': ~e ~~e:;el !~e~ cr ...

Predicting the oral uptake efficiency of chemicals in mammals: Combining the hydrophilic and lipophilic range

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

O'Connor, Isabel A., E-mail: i.oconnor@science.ru.nl; Huijbregts, Mark A.J., E-mail: m.huijbregts@science.ru.nl; Ragas, Ad M.J., E-mail: a.ragas@science.ru.nl

Environmental risk assessment requires models for estimating the bioaccumulation of untested compounds. So far, bioaccumulation models have focused on lipophilic compounds, and only a few have included hydrophilic compounds. Our aim was to extend an existing bioaccumulation model to estimate the oral uptake efficiency of pollutants in mammals for compounds over a wide K{sub ow} range with an emphasis on hydrophilic compounds, i.e. compounds in the lower K{sub ow} range. Usually, most models use octanol as a single surrogate for the membrane and thus neglect the bilayer structure of the membrane. However, compounds with polar groups can have different affinitiesmore » for the different membrane regions. Therefore, an existing bioaccumulation model was extended by dividing the diffusion resistance through the membrane into an outer and inner membrane resistance, where the solvents octanol and heptane were used as surrogates for these membrane regions, respectively. The model was calibrated with uptake efficiencies of environmental pollutants measured in different mammals during feeding studies combined with human oral uptake efficiencies of pharmaceuticals. The new model estimated the uptake efficiency of neutral (RMSE = 14.6) and dissociating (RMSE = 19.5) compounds with logK{sub ow} ranging from − 10 to + 8. The inclusion of the K{sub hw} improved uptake estimation for 33% of the hydrophilic compounds (logK{sub ow} < 0) (r{sup 2} = 0.51, RMSE = 22.8) compared with the model based on K{sub ow} only (r{sup 2} = 0.05, RMSE = 34.9), while hydrophobic compounds (logK{sub ow} > 0) were estimated equally by both model versions with RMSE = 15.2 (K{sub ow} and K{sub hw}) and RMSE = 15.7 (K{sub ow} only). The model can be used to estimate the oral uptake efficiency for both hydrophilic and hydrophobic compounds. -- Highlights: ► A mechanistic model was developed to estimate oral uptake efficiency. ► Model covers wide logK{sub ow} range (- 10 to + 8) and several mammalian species. ► K{sub ow} and the heptane water partition coefficient K{sub hw} were combined. ► K{sub ow} and K{sub hw} reflect the inner and the outer membrane diffusion resistance. ► Combining K{sub ow} and K{sub hw} improved uptake estimation for hydrophilic compounds.« less

Polar organic chemical integrative sampler (POCIS) uptake rates for 17 polar pesticides and degradation products: laboratory calibration.

PubMed

Ibrahim, Imtiaz; Togola, Anne; Gonzalez, Catherine

2013-06-01

Polar organic chemical integrative samplers (POCIS) are useful for monitoring a wide range of chemicals, including polar pesticides, in water bodies. However, few calibration data are available, which limits the use of these samplers for time-weighted average concentration measurements in an aquatic medium. This work deals with the laboratory calibration of the pharmaceutical configuration of a polar organic chemical integrative sampler (pharm-POCIS) for calculating the sampling rates of 17 polar pesticides (1.15 ≤  logK(ow) ≤ 3.71) commonly found in water. The experiment, conducted for 21 days in a continuous water flow-through exposure system, showed an integrative accumulation of all studied pesticides for 15 days. Three compounds (metalaxyl, azoxystrobine, and terbuthylazine) remained integrative for the 21-day experiment. The sampling rates measured ranged from 67.9 to 279 mL day(-1) and increased with the hydrophobicity of the pesticides until reaching a plateau where no significant variation in sampling rate is observed when increasing the hydrophobicity.

Polychlorinated biphenyl concentrations, congener profiles, and ratios in the fat tissue, eggs, and plasma of snapping turtles (Chelydra s. serpentina) from the Ohio Basin of Lake Erie, USA.

PubMed

Dabrowska, H; Fisher, S W; Estenik, J; Kidekhel, R; Stromberg, P

2006-08-01

Concentrations and profiles of polychlorinated biphenyls (PCBs) were determined in three tissues of adult snapping turtles (Chelydra serpentina serpentina) from six locations in the Ohio Basin of Lake Erie to characterize tissue variation and geographic trends. The locations included the Ohio Areas of Concern, i.e., the Ashtabula, Black, and Maumee Rivers; the Ottawa River near Toledo; and two reference sites. Mean total PCBs were greatest in turtles from the Ottawa River followed by the Maumee, Ashtabula, and Black Rivers. All three types of samples-fat tissue (FT), eggs, and plasma-showed the same geographic trend in PCB levels. On a wet-weight basis, mean concentrations ranged from 2,148 to 18,669 ng/g in FT, from 183 to 3,683 ng/g in eggs, and from 18 to 201 ng/g in plasma. Across all sites, total PCB concentrations between the tissues were significantly correlated (0.001 < p < 0.005; Pearson correlation coefficient (r ( P )) was between 0.720 and 0.954). Two distinctly different profiles with respect to relative congener and homologue concentrations were found among the sites. One that included four of the six sites examined was characterized by hexa-chlorobiphenyl (hexa-CB) dominance followed by hepta-CBs, with PCBs no. 138 + 163, 153 + 132 + 105, and 180 being the most abundant congeners. The second profile, specific for turtles from the Ottawa River, was different from the first in that tetra-CBs were the most abundant congeners followed by hexa-CBs. Analysis of variance (ANOVA) indicated significant intertissue differences in the PCB homologue profiles, i.e., FT had a higher percentage of hepta-, octa-, and nona-CBs compared with eggs and plasma, whereas eggs showed a higher percentage of hexa-CBs. At any listed location, FT, eggs, and plasma had the same congener profile. An intertissue distribution of lipid-normalized individual congener concentrations examined by regression analyses revealed significant egg-FT, egg-plasma, and FT-plasma relations for >40 congeners (0.001 < p < 0.05). The distribution ratios determined for these congeners from the slope of the regression lines averaged 1.235 +/- 0.279, 0.430 +/- 0.170, and 0.387 +/- 0.115, respectively. The plasma wet weight-FT lipid-normalized concentration ratios for these congeners averaged 0.012 +/- 0.006. Both egg-FT and plasma wet weight-FT lipid-normalized ratios regressed against log K(ow) showed significant decreases, with increasing log K(ow), indicating greater accumulation of highly chlorinated congeners in FT than in other compartments. The estimated 2,3,7,8-tetrachlorodibenzo-p-dioxin toxic equivalents ranged from 0.007 ng/g at reference sites to 0.060 ng/g at contaminated sites and from 0.099 to 1.992 ng/g in plasma and eggs, respectively. In both plasma and eggs, coplanar-CBs were the major contributors to total toxic equivalents (TEQs). Eggs from all contaminated sites had TEQs that exceeded the lowest observed effect level TEQs proposed for bald eagle chicks, in addition to high SigmaPCB levels at some of these sites, especially the Ottawa and Maumee River sites, indicate potentially increased risk to turtles and possibly other wildlife species inhabiting these ecosystems. Significant correlations of total PCBs and individual congeners between FT, eggs, and plasma indicate that blood sampling can provide a good nonlethal measure of PCB exposure and can be used to monitor environmental contamination.

Development and evaluation of predictive model for bovine serum albumin-water partition coefficients of neutral organic chemicals.

PubMed

Ma, Guangcai; Yuan, Quan; Yu, Haiying; Lin, Hongjun; Chen, Jianrong; Hong, Huachang

2017-04-01

The binding of organic chemicals to serum albumin can significantly reduce their unbound concentration in blood and affect their biological reactions. In this study, we developed a new QSAR model for bovine serum albumin (BSA) - water partition coefficients (K BSA/W ) of neutral organic chemicals with large structural variance, logK BSA/W values covering 3.5 orders of magnitude (1.19-4.76). All chemical geometries were optimized by semi-empirical PM6 algorithm. Several quantum chemical parameters that reflect various intermolecular interactions as well as hydrophobicity were selected to develop QSAR model. The result indicates the regression model derived from logK ow , the most positive net atomic charges on an atom, Connolly solvent excluded volume, polarizability, and Abraham acidity could explain the partitioning mechanism of organic chemicals between BSA and water. The simulated external validation and cross validation verifies the developed model has good statistical robustness and predictive ability, thus can be used to estimate the logK BSA/W values for chemicals in application domain, accordingly to provide basic data for the toxicity assessment of the chemicals. Copyright © 2016 Elsevier Inc. All rights reserved.

Substituted benzotriazoles as inhibitors of copper corrosion in borate buffer solutions

NASA Astrophysics Data System (ADS)

Agafonkina, M. O.; Andreeva, N. P.; Kuznetsov, Yu. I.; Timashev, S. F.

2017-08-01

The adsorption of substituted 1,2,3-benzotriazoles (R-BTAs) onto copper is measured via ellipsometry in a pure borate buffer (pH 7.4) and satisfactorily described by Temkin's isotherm. The adsorption free energy (-Δ G a 0 ) values of these azoles are determined. The (-Δ G a 0 ) values are found to rise as their hydrophobicity, characterized by the logarithm of the partition coefficient of a substituted BTA in a model octanol-water system (log P), grows. The minimum concentration sufficient for the spontaneous passivation of copper ( C min) and a shift in the potential of local copper depassivation with chlorides ( E pt) after an azole is added to the solution (i.e., Δ E = E pt in - E pt backgr characterizing the ability of its adsorption to stabilize passivation) are determined in the same solution containing a corrosion additive (0.01M NaCl) for each azole under study. Both criteria of the passivating properties of azoles (log C min and Δ E) are shown to correlate linearly with log P, testifying to the role played by surface activity of this family of organic inhibitors in protecting copper in an aqueous solution.

Released fraction of polychlorinated biphenyls from soil-biosolid system using a leaching procedure and its comparison with bioavailable fraction determined by wheat plant uptake.

PubMed

Jachero, Lourdes; Leiva, Claudio; Ahumada, Inés; Richter, Pablo

2017-11-01

The bioavailability of polychlorinated biphenyls (PCBs) in soils amended with biosolids was estimated using an aqueous leaching process of the compounds combined with rotating disk sorptive extraction (RDSE), and compared with bioavailability determined through of PCB absorption in wheat plants growing in the same soil-biosolid matrix. The matrices consisted of soil amended with biosolids at doses of 30, 90, and 200 Mg/ha, which increase concomitantly the organic matter content of the matrix. Considering that PCBs were natively absent in both the biosolids and soil used, the compounds were spiked in the biosolids and aged for 10 days. For each biosolid dose, the aqueous leaching profile was studied and equilibrium time was calculated to be 33 h. The leaching fractions determined by RDSE, considering total PCBs studied, were 12, 7, and 6% and the bioavailable fractions absorbed by the wheat root were found to be 0.5, 0.3, and 0.2% for 30, 90, and 200 Mg/ha doses, respectively. Both fractions leachable and bioavailable decrease with both increasing hydrophobicity of the compound (Kow) and increasing in the biosolid dose. It was found that both fractions (leaching and bioavailable) correlated according to the bivariate least squares regression, represented by a coefficient of correlation of 0.86. Therefore, the application of the chemical method involving a leaching procedure is an alternative to estimate the bioavailable fraction of PCBs in wheat plants in a simpler and in a shorter time.

Organotin compounds and aquatic bacteria: A review

NASA Astrophysics Data System (ADS)

Cooney, J. J.

1995-03-01

Organotins are toxic to microorganisms. Trisubstituted organotins (R3SnX) are considered more toxic than disubstituted (R2SnX2) or monosubstituted (RSnX3) compounds, and tetrasubstituted compounds (R4Sn) are not considered toxic. In the R3Sn series propyl-, butyl-, pentyl-, phenyl- and cyclohexyltins are the most toxic to microorganisms. Toxicity towards aerobes in the R3Sn series is related to total molecular surface area and to the octanol: water partition coefficient, Kow, which is a measure of hydrophobicity. Care must be taken when testing the toxicity of tin compounds in the laboratory, for a number of biological, chemical and physical factors can influence the apparent toxicity. Although TBT is generally the most toxic of the butyltins, there are instances where monobutyltin (MBT) is as toxic, or more toxic, than TBT to microorganisms. Thus, debutylation in the sequence TBT→DBT→MBT→Sn does not detoxity TBT for all microorganisms. Some microorganisms can methylate inorganic or organic tins under aerobic or anaerobic conditions. Methylation can also occur by chemical means and the relative contributions of biotic and abiotic mechanisms are not clear. It is difficult to isolate a pure culture which can methylate tin compounds aerobically, and it is difficult to isolate a pure culture which degrades TBT, suggesting that microbial consortiums may be involved in transformations of organotins in the aquatic environment. Methylation and debutylation alter the adsorbtivity and solubility of tin compounds; thus microorganisms can influence the environmental mobility of tin. TBT-resistant microorganisms can be isolated, and in some of them resistance to TBT can be plasmid-mediated.

Characterization of the biosorption and biodegradation properties of Ensifer adhaerens: A potential agent to remove polychlorinated biphenyls from contaminated water.

PubMed

Xu, Li; Chen, Xiong; Li, Huixin; Hu, Feng; Liang, Mingxiang

2016-01-25

Ensifer adhaerens is a soil bacterium known for its potential to remove pollutants from the environment. We investigated the contributions of biosorption and biodegradation to the process of polychlorinated biphenyl (PCB) removal from water by living or heat-killed E. adhaerens with different incubation times. We examined the physicochemical properties of E. adhaerens, including its membrane surface moieties, extracellular polymeric substances, and defense-related enzyme activities. In addition, we measured the biosorption and biodegradation of different PCB congeners. We found that removal of PCBs by heat-killed E. adhaerens was attributed to biosorption only, while both biosorption and biodegradation were responsible for the dissipation of PCBs by live E. adhaerens. Biosorption initially plays a major role in PCB removal, but biodegradation becomes increasingly important with increased incubation time. The results of infrared spectroscopy analysis showed that bacterial lipids, proteins, and polysaccharides, which offer abundant binding sites, are responsible for the biosorption of PCBs. Biodegradation was correlated with loosely bound polysaccharides and defense-related enzyme activities that could increase the pollutant's solubility and facilitate further degradation. The PCB congeners exhibited different biosorption and biodegradation patterns, and the patterns were correlated with the octanol-water partition coefficients (Kow) of the congeners. The more hydrophobic organic compounds tended to have higher biosorption, but lower biodegradation capacities. These results indicate that E. adhaerens-mediated biosorption and biodegradation of PCBs are dependent on the status of the strain, the incubation time, and the PCB congener present, and suggest guidelines for PCB removal from water. Copyright © 2015 Elsevier B.V. All rights reserved.

Determination of 1-octanol-air partition coefficient using gaseous diffusion in the air boundary layer.

PubMed

Ha, Yeonjeong; Kwon, Jung-Hwan

2010-04-15

Exact determination of the partition coefficient between 1-octanol and air (K(OA)) is very important because it is a key descriptor for describing the thermodynamic partitioning between the air and organic phases. In spite of its importance, the number and quality of experimental K(OA) values for hydrophobic organic chemicals are limited because of experimental difficulties. Thus, to measure K(OA) values, a high-throughput method was developed that used liquid-phase extraction with 1-octanol drop at the tip of a microsyringe needle. The concentration in the headspace surrounding the 1 muL octanol drop was equilibrated with liquid octanol containing polycyclic aromatic hydrocarbons (PAHs). The change in concentrations of PAHs in the octanol drop was measured to obtain mass transfer rate constants, and these rate constants were then converted into K(OA) values using a film diffusion model. Thirteen polycyclic aromatic hydrocarbons with log K(OA) between 5 and 12 were chosen for the proof of the principle. Experimental determination of log K(OA) was accomplished in 30 h for PAHs with their log K(OA) less than 11. The measured log K(OA) values were very close to those obtained by various experimental and estimation methods in the literature, suggesting that this new method can provide a fast and easy determination of log K(OA) values for many chemicals of environmental interests. In addition, the applicability of the method can be extended to determine Henry's law constant for compounds with low vapor pressure and to estimate gaseous transfer rate of semivolatile compounds for environmental fate modeling.

Attack pattern of Platypus koryoensis (Coleoptera: Curculionidae: Platypodidae) in relation to crown dieback of Mongolian oak in Korea

Treesearch

Jung-Su Lee; Robert A. Haack; Won Il. Choi

2011-01-01

The ambrosia beetle, Platypus koryoensis (Murayama), vectors the Korean oak wilt (KOW) pathogen, Raffaelea quercus-mongolicae K.H. Kim, Y.J. Choi, & H.D. Shin, in Korea, which is highly lethal to Mongolian oak, Quercus mongolica Fisch., and is considered a major threat to forest ecosystem health. We...

Inactivation of viruses using novel protein A wash buffers.

PubMed

Bolton, Glen R; Selvitelli, Keith R; Iliescu, Ionela; Cecchini, Douglas J

2015-01-01

Low pH viral inactivation is typically performed in the eluate pool following the protein A capture step during the manufacturing of monoclonal antibodies and Fc-fusion proteins. However, exposure to low pH has the potential to alter protein quality. To avoid these difficulties, novel wash buffers capable of inactivating viruses while antibodies or Fc-fusion proteins were bound to protein A or mixed mode resins were developed. By equilibrating the column in high salt buffer (2 M ammonium sulfate or 3 M sodium chloride) after loading, the hydrophobic interactions between antibodies and protein A ligands were increased enough to prevent elution at pH 3. The ammonium sulfate was also found to cause binding of an antibody to a mixed mode cation exchange and a mixed mode anion exchange resin at pH values that caused elution in conventional cation and anion exchange resins (pH 3.5 for Capto Adhere and pH 8.0 for Capto MMC), indicating that retention was due to enhanced hydrophobic interactions. The potential of the 2 M ammonium sulfate pH 3 buffer, a 1 M arginine buffer, and a buffer containing the detergent LDAO to inactivate XMuLV virus when used as protein A wash buffers with a 1 hour contact time were studied. The high salt and detergent containing wash buffers provided about five logs of removal, determined using PCR, and complete combined removal and inactivation (> 6 logs), determined by measuring infectivity. The novel protein A washes could provide more rapid, automated viral inactivation steps with lower pool conductivities. © 2014 American Institute of Chemical Engineers.

Wide-pore silica-based ether-bonded phases for separation of proteins by high-performance hydrophobic-interaction and size-exclusion chromatography.

PubMed

Miller, N T; Feibush, B; Karger, B L

1984-12-21

This paper examines the use of wide-pore silica-based hydrophilic ether-bonded phases for the chromatographic separation of proteins under mild elution conditions. In particular, ether phases of the following structure identical to Si-(CH2)3-O-(CH2-CH2-O)n-R, where n = 1, 2, 3 and R = methyl, ethyl or n-butyl, have been prepared. These phases can be employed either in high-performance hydrophobic-interaction or size-exclusion chromatography, depending on mobile phase conditions. In the hydrophobic-interaction mode, a gradient of decreasing salt concentration, e.g., from 3 M ammonium sulfate (pH 6.0, 25 degrees C), yields sharp peaks with high mass recovery of active proteins. In this mode, retention can be controlled by salt type and concentration, as well as by column temperature. In the size-exclusion mode, use of medium ionic strength, e.g., 0.5 M ammonium acetate (pH 6.0) yields linear calibration of log (MW[eta]) vs. retention volume. Even at 0.05 M salt concentration, no stationary phase charge effects on protein elution are observed. These bonded-phase columns exhibit good column-to-column reproducibility and constant retention for at least five months of continual use. Examples of the high-performance separation of proteins in both modes are illustrated.

Including Bioconcentration Kinetics for the Prioritization and Interpretation of Regulatory Aquatic Toxicity Tests of Highly Hydrophobic Chemicals.

PubMed

Kwon, Jung-Hwan; Lee, So-Young; Kang, Hyun-Joong; Mayer, Philipp; Escher, Beate I

2016-11-01

Worldwide, regulations of chemicals require short-term toxicity data for evaluating hazards and risks of the chemicals. Current data requirements on the registration of chemicals are primarily based on tonnage and do not yet consider properties of chemicals. For example, short-term ecotoxicity data are required for chemicals with production volume greater than 1 or 10 ton/y according to REACH, without considering chemical properties. Highly hydrophobic chemicals are characterized by low water solubility and slow bioconcentration kinetics, which may hamper the interpretation of short-term toxicity experiments. In this work, internal concentrations of highly hydrophobic chemicals were predicted for standard acute ecotoxicity tests at three trophic levels, algae, invertebrate, and fish. As demonstrated by comparison with maximum aqueous concentrations at water solubility, chemicals with an octanol-water partition coefficient (K ow ) greater than 10 6 are not expected to reach sufficiently high internal concentrations for exerting effects within the test duration of acute tests with fish and invertebrates, even though they might be intrinsically toxic. This toxicity cutoff was explained by the slow uptake, i.e., by kinetics, not by thermodynamic limitations. Predictions were confirmed by data entries of the OECD's screening information data set (SIDS) (n = 746), apart from a few exceptions concerning mainly organometallic substances and those with inconsistency between water solubility and K ow . Taking error propagation and model assumptions into account, we thus propose a revision of data requirements for highly hydrophobic chemicals with log K ow > 7.4: Short-term toxicity tests can be limited to algae that generally have the highest uptake rate constants, whereas the primary focus of the assessment should be on persistence, bioaccumulation, and long-term effects.

Empirical, thermodynamic and quantum-chemical investigations of inclusion complexation between flavanones and (2-hydroxypropyl)-cyclodextrins.

PubMed

Liu, Benguo; Li, Wei; Nguyen, Tien An; Zhao, Jian

2012-09-15

The inclusion complexation of (2-hydroxypropyl)-cyclodextrins with flavanones was investigated by phase solubility measurements, as well as thermodynamic and quantum chemical methods. Inclusion complexes were formed between (2-hydroxypropyl)-α-cyclodextrin (HP-α-CD), (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD), (2-hydroxypropyl)-γ-cyclodextrin (HP-γ-CD) and β-cyclodextrin (β-CD) and four flavanones (naringenin, naringin, hesperetin and dihydromyricetin) in aqueous solutions and their phase solubility was determined. For all the flavanones, the stability constants of their complexes formed with different CDs followed the rank order: HP-β-CD (MW 1540)>HP-β-CD (MW 1460)>HP-β-CD (MW 1380)>β-CD>HP-γ-CD>HP-α-CD. Experimental results and quantum chemical calculations showed that the ability of flavanones to form inclusion complex with (2-hydroxypropyl)-cyclodextrins was determined by both the steric effect and hydrophobicity of the flavanones. For flavanones that have similar molecular volumes, the hydrophobicity of the molecule was the main determining factor of its ability to form inclusion complexes with HP-β-CD, and the hydrophobicity parameter Log P is highly correlated with the stability constant of the complexes. Results of thermodynamic study demonstrated that hydrophobic interaction is the main driving force for the formation process of the flavanone-CD inclusion complexes. Quantum chemical analysis of the most active hydroxyl groups and HOMO (the highest occupied molecular orbital) showed that the B ring of the flavanones was most likely involved in hydrogen bonding with the side groups in the cavity of the CDs, through which the inclusion complex was stabilised. Copyright © 2012 Elsevier Ltd. All rights reserved.

Permeation-Enhancing Effects and Mechanisms of Borneol and Menthol on Ligustrazine: A Multiscale Study using In Vitro and Coarse-Grained Molecular Dynamics Simulation Methods.

PubMed

Dai, Xingxing; Wang, Ran; Wu, Zhimin; Guo, Shujuan; Yang, Chang; Ma, Lina; Chen, Liping; Shi, Xinyuan; Qiao, Yanjiang

2018-06-20

Borneol (BO) and menthol (MEN) are two widely used natural permeation enhancers in the transdermal drug delivery system. In previous studies, their permeation enhancement effects and mechanisms of action on the hydrophobic drug osthole (logP=3.8) and hydrophilic drug 5-fluorouracil (logP=-0.9) have been studied. In this study, ligustrazine (LTZ), whose logP is 1.3, was used as a model drug to provide a comprehensive understanding of the influence of its logP on the permeation-enhancing effects of BO and MEN. Both BO and MEN enhanced the permeation of LTZ through the skin stratum corneum, as determined using the modified Franz diffusion cell experiment. The enhancement mechanisms were illustrated by coarse-grained molecular dynamics simulations as follows: at low concentrations, the enhancing ratio of MEN was higher than that of BO because of the stronger perturbation effects of MEN on the lipid bilayer, making it looser and facilitating LTZ diffusion. However, at high concentrations, in addition to the diffusion mechanism, BO induced the formation of water channels to improve the permeation of LTZ; however, MEN had no significant effects through this mechanism. Their results were different from those found with osthole and 5-fluorouracil and have been discussed in this paper. This article is protected by copyright. All rights reserved. This article is protected by copyright. All rights reserved.

MLP Tools: a PyMOL plugin for using the molecular lipophilicity potential in computer-aided drug design

NASA Astrophysics Data System (ADS)

Oberhauser, Nils; Nurisso, Alessandra; Carrupt, Pierre-Alain

2014-05-01

The molecular lipophilicity potential (MLP) is a well-established method to calculate and visualize lipophilicity on molecules. We are here introducing a new computational tool named MLP Tools, written in the programming language Python, and conceived as a free plugin for the popular open source molecular viewer PyMOL. The plugin is divided into several sub-programs which allow the visualization of the MLP on molecular surfaces, as well as in three-dimensional space in order to analyze lipophilic properties of binding pockets. The sub-program Log MLP also implements the virtual log P which allows the prediction of the octanol/water partition coefficients on multiple three-dimensional conformations of the same molecule. An implementation on the recently introduced MLP GOLD procedure, improving the GOLD docking performance in hydrophobic pockets, is also part of the plugin. In this article, all functions of the MLP Tools will be described through a few chosen examples.

Augmented multivariate image analysis applied to quantitative structure-activity relationship modeling of the phytotoxicities of benzoxazinone herbicides and related compounds on problematic weeds.

PubMed

Freitas, Mirlaine R; Matias, Stella V B G; Macedo, Renato L G; Freitas, Matheus P; Venturin, Nelson

2013-09-11

Two of major weeds affecting cereal crops worldwide are Avena fatua L. (wild oat) and Lolium rigidum Gaud. (rigid ryegrass). Thus, development of new herbicides against these weeds is required; in line with this, benzoxazinones, their degradation products, and analogues have been shown to be important allelochemicals and natural herbicides. Despite earlier structure-activity studies demonstrating that hydrophobicity (log P) of aminophenoxazines correlates to phytotoxicity, our findings for a series of benzoxazinone derivatives do not show any relationship between phytotoxicity and log P nor with other two usual molecular descriptors. On the other hand, a quantitative structure-activity relationship (QSAR) analysis based on molecular graphs representing structural shape, atomic sizes, and colors to encode other atomic properties performed very accurately for the prediction of phytotoxicities of these compounds against wild oat and rigid ryegrass. Therefore, these QSAR models can be used to estimate the phytotoxicity of new congeners of benzoxazinone herbicides toward A. fatua L. and L. rigidum Gaud.

Validity and validation of expert (Q)SAR systems.

PubMed

Hulzebos, E; Sijm, D; Traas, T; Posthumus, R; Maslankiewicz, L

2005-08-01

At a recent workshop in Setubal (Portugal) principles were drafted to assess the suitability of (quantitative) structure-activity relationships ((Q)SARs) for assessing the hazards and risks of chemicals. In the present study we applied some of the Setubal principles to test the validity of three (Q)SAR expert systems and validate the results. These principles include a mechanistic basis, the availability of a training set and validation. ECOSAR, BIOWIN and DEREK for Windows have a mechanistic or empirical basis. ECOSAR has a training set for each QSAR. For half of the structural fragments the number of chemicals in the training set is >4. Based on structural fragments and log Kow, ECOSAR uses linear regression to predict ecotoxicity. Validating ECOSAR for three 'valid' classes results in predictivity of > or = 64%. BIOWIN uses (non-)linear regressions to predict the probability of biodegradability based on fragments and molecular weight. It has a large training set and predicts non-ready biodegradability well. DEREK for Windows predictions are supported by a mechanistic rationale and literature references. The structural alerts in this program have been developed with a training set of positive and negative toxicity data. However, to support the prediction only a limited number of chemicals in the training set is presented to the user. DEREK for Windows predicts effects by 'if-then' reasoning. The program predicts best for mutagenicity and carcinogenicity. Each structural fragment in ECOSAR and DEREK for Windows needs to be evaluated and validated separately.

Evaluating the precision of passive sampling methods using ...

EPA Pesticide Factsheets

To assess these models, four different thicknesses of low-density polyethylene (LDPE) passive samplers were co-deployed for 28 days in the water column at three sites in New Bedford Harbor, MA, USA. Each sampler was pre-loaded with six PCB performance reference compounds (PRCs) to assess equilibrium status, such that the percent of PRC lost would range depending on PRC and LDPE thickness. These data allow subsequent Cfree comparisons to be made in two ways: (1) comparing Cfree derived from one thickness using different models and (2) comparing Cfree derived from the same model using different thicknesses of LDPE. Following the deployments, the percent of PRC lost ranged from 0-100%. As expected, fractional equilibrium decreased with increasing PRC molecular weight as well as sampler thickness. Overall, a total of 27 PCBs (log KOW ranging from 5.07 – 8.09) were measured at Cfree concentrations varying from 0.05 pg/L (PCB 206) to about 200 ng/L (PCB 28) on a single LDPE sampler. Relative standard deviations (RSDs) for total PCB measurements using the same thickness and varying model types range from 0.04-12% and increased with sampler thickness. Total PCB RSD for measurements using the same model and varying thickness ranged from: 6 – 30%. No RSD trends between models were observed but RSD did increase as Cfree decreased. These findings indicate that existing models yield precise and reproducible results when using LDPE and PRCs to measure Cfree. This work in

Application of nanofiltration for the removal of carbamazepine, diclofenac and ibuprofen from drinking water sources.

PubMed

Vergili, I

2013-09-30

Pharmaceutical active compounds (PhACs) are persistent during the process used to treat drinking water and, because drinking water treatment plants are not specifically designed to remove PhACs, these compounds are found in drinking water. Although there are currently no regulations or drinking water directives for PhACs, precautionary principles suggest ensuring maximal removal of PhACs through improved or existing treatment techniques. This study was designed to investigate the performance of a nanofiltration membrane in cross-flow filtration equipment for the removal of three PhACs [carbamazepine (CBZ), diclofenac (DIC) and ibuprofen (IBU)] that were spiked in water taken from a drinking water treatment plant using surface water. Because of their low solubilities, high log Kow values, low dipole moments and negative charges, higher rejection values were obtained for DIC and IBU. Low to moderate rejection values were most likely due to the small molecular sizes of the PhACs (i.e., MW < MWCO) and the divalent ions present in the raw water. Flux declines obtained from DIC studies was attributed to the adsorption of DIC ions inside the membrane pores, which decreases the flux. The most evident change in the FT-IR spectrum after nanofiltration was the appearance of new intense bands at 1072 cm(-1) and 1011 cm(-1), indicating the deposition of calcium salts on the membrane surface. Copyright © 2013 Elsevier Ltd. All rights reserved.

Integrating Monitoring and Genetic Methods To Infer Historical Risks of PCBs and DDE to Common and Roseate Terns Nesting Near the New Bedford Harbor Superfund Site (Massachusetts, USA).

PubMed

Nacci, Diane E; Hahn, Mark E; Karchner, Sibel I; Jayaraman, Saro; Mostello, Carolyn; Miller, Kenneth M; Blackwell, Carma Gilchrist; Nisbet, Ian C T

2016-09-20

Common and roseate terns are migratory piscivorous seabirds with major breeding colonies within feeding range of the polychlorinated biphenyl (PCB)-contaminated New Bedford Harbor (NBH, MA, USA) Superfund site. Our longitudinal study shows that before PCB discharges into NBH ceased (late 1970s), tern eggs had very high but variable PCB concentrations. However, egg concentrations of PCBs as well as DDE (1,1-bis(p-chlorophenyl)-2,2-dichloroethene), the degradation product of the ubiquitous global contaminant DDT (1,1,1-trichloro-2,2-bis(p-chlorophenyl) ethane), have since declined. Rate constants for temporal decline of PCB congeners in tern eggs varied inversely with log10KOW (n-octanol-water partition coefficient), shifting egg congener patterns away from those characterizing NBH sediment. To estimate the toxic effects on tern eggs of PCB dioxin-like congener (DLC) exposures, we extrapolated published laboratory data on common terns to roseate terns by characterizing genetic and functional similarities in species aryl hydrocarbon receptors (AHRs), which mediate DLC sensitivity. Our assessment of contaminant risks suggests that terns breeding near NBH were exposed historically to toxic levels of PCBs and DDE; however, acute effects on tern egg development have become less likely since the 1970s. Our approach demonstrates how comparative genetics at target loci can effectively increase the range of inference for chemical risk assessments from tested to untested and untestable species.

What determines skin sensitization potency: Myths, maybes ...

EPA Pesticide Factsheets

It is widely considered to be a self-evident truth that substances must have a molecular weight (MW) less than 500 to effectively penetrate through the skin in order to induce sensitisation. However, Roberts et al. 2010, evaluated a data set of 699 substances taken from the TIMES-SS expert system and identified that of the 13 substances with a MW above 500, 5 were reported as skin sensitisers. This provided good evidence to refute such a MW threshold. The present study set about compiling a larger and more diverse set of substances such as those evaluated for their skin sensitisation potential under the EU REACH regulation. A dataset of 2575 substances that had been tested for skin sensitisation, using guinea pigs and/or mice was collected. The dataset contained 197 substances with a MW>500: 33 of these were categorised as skin sensitisers. Each of the 33 substances were then evaluated in turn – metal containing complexes, reaction products and mixtures were excluded from further consideration. The final set of 14 sensitisers with a MW>500 were considered on the basis of their reaction chemistry to propose likely mechanistic explanations for their sensitisation behaviour. Penetration ability is correlated with MW (and LogKow): if the MW threshold is shown to be inapplicable for skin sensitisation potency, in turn it also indicates that penetration is not a relevant parameter for skin sensitisation. Exercise to search and extract REACH data for the skin se

Insight into the adsorption mechanisms of trace organic carbon on biological treatment process.

PubMed

Zolfaghari, Mehdi; Drogui, Patrick; Brar, Satinder Kaur; Buelna, Gerardo; Dubé, Rino

2017-09-01

The presence of recalcitrant dissolved organic matter (DOM) could have a significant effect on the adsorption mechanism and capacity of the sludge for many trace organic carbons (TrOCs). In this study, adsorption of three TrOCs on the sludge and HA was investigated. The results revealed that neutral hydrophilic compounds had an insignificant interaction with both sludge and HA. Positively charged compounds, such as fluoranthene, had more affinity toward HA than sludge with solid/liquid partitioning of 57 and 3.2 L/g, respectively. The adsorption intensity (K f ) of di-2-ethyl hexyl phthalate was 0.5 and 1.13 for the HA and the sludge, respectively. By introducing the sludge to the solution of HA and TrOCs that already reached equilibrium, the sludge adsorption capacity in the presence of HA was investigated. The finding showed that at the lower concentration, adsorption of HA on the sludge was considered as the main removal pathway for the adsorbed emerging contaminants, as 70 mg of HA was adsorbed by a gram of sludge. For the higher concentration, desorption of TrOCs from DOM into the sludge comprised 15-30% of total removal efficiency. CBZ: carbamazepine; DEHP: di-2-ethyl hexyl phthalate; DOM: dissolved organic matter; FLAN: fluoranthene; f oc : fraction of organic carbon; HA: humic acid; Log Kow: octanol-water partition coefficient; PAH: polycyclic aromatic hydrocarbon TS: total solid; TrOCs: trace organic carbons VS: volatile solid.

Effectiveness of dishwashing liquids in removing chlorothalonil and chlorpyrifos residues from cherry tomatoes.

PubMed

Wang, Zhiwei; Huang, Jiexun; Chen, Jinyuan; Li, Feili

2013-08-01

Washing is the most practical way to remove pesticide residues in fruits and vegetables. Two commonly used kitchen dishwashing liquids (detergents) in Chinese market were tested for enhanced removal of chlorpyrifos (CHP) and chlorothalonil (CHT) in cherry tomatoes by soaking the cherry tomatoes in the detergent solutions. The critical micelle concentrations of detergent A and detergent B were about 250 mg L(-1) and 444 mg L(-1), respectively. Detergent A had a higher solubilizing ability for pesticides and hence washing effectiveness than detergent B. The apparent solubility of CHP increased with increasing detergent concentration, while that of CHT remained comparatively invariant independent of detergent concentration within the tested range. The apparent solubility of CHP was also consistently higher in solutions of both detergents as compared to CHT. Due probably to its lower logKow value, CHT was more readily washed off cherry tomatoes than CHP. In terms of washing, a duration of 10-20 min was sufficient for removal of pesticides on cherry tomatoes in distilled water and detergent solutions. The effectiveness of removing pesticides increased with increasing detergent concentration from 50 mg L(-1) to 5 g L(-1), with up to 80% CHT and 42% CHP removed. Multiple washing further increased pesticide removal. Adding 10% acetic acid to lower pH or increasing washing temperature favored pesticide removal, but 10% NaCl produced the shielding effect and substantially reduced the effectiveness of detergent A for pesticide removal. Copyright © 2013 Elsevier Ltd. All rights reserved.

Calibration and use of the polar organic chemical integrative sampler--a critical review.

PubMed

Harman, Christopher; Allan, Ian John; Vermeirssen, Etiënne L M

2012-12-01

The implementation of strict environmental quality standards for polar organic priority pollutants poses a challenge for monitoring programs. The polar organic chemical integrative sampler (POCIS) may help to address the challenge of measuring low and fluctuating trace concentrations of such organic contaminants, offering significant advantages over traditional sampling. In the present review, the authors evaluate POCIS calibration methods and factors affecting sampling rates together with reported environmental applications. Over 300 compounds have been shown to accumulate in POCIS, including pesticides, pharmaceuticals, hormones, and industrial chemicals. Polar organic chemical integrative sampler extracts have been used for both chemical and biological analyses. Several different calibration methods have been described, which makes it difficult to directly compare sampling rates. In addition, despite the fact that some attempts to correlate sampling rates with the properties of target compounds such as log K(OW) have been met with varying success, an overall model that can predict uptake is lacking. Furthermore, temperature, water flow rates, salinity, pH, and fouling have all been shown to affect uptake; however, there is currently no robust method available for adjusting for these differences. Overall, POCIS has been applied to a wide range of sampling environments and scenarios and has been proven to be a useful screening tool. However, based on the existing literature, a more mechanistic approach is required to increase understanding and thus improve the quantitative nature of the measurements. Copyright © 2012 SETAC.

Evaluation of low-cost disposable polymeric materials for sorptive extraction of organic pollutants in water samples.

PubMed

Prieto, Ailette; Rodil, Rosario; Quintana, José Benito; Rodríguez, Isaac; Cela, Rafael; Möder, Monika

2012-02-24

The capabilities of four commercially available and low cost polymeric materials for the extraction of polar and non-polar contaminants (logK(ow)=-0.07-6.88, from caffeine to octocrylene, respectively) from water samples was compared. Tested sorbents were polyethersulphone, polypropylene and Kevlar, compared to polydimethylsiloxane as reference material. Parameters that affect the extraction process such as pH and ionic strength of the sample, extraction time and desorption conditions were thoroughly investigated. A set of experimental partition coefficients (K(pw)), at two different experimental conditions, was estimated for the best suited materials and compared with the theoretical octanol-water (K(ow)) partition coefficients of the analytes. Polyethersulphone displayed the largest extraction yields for both polar and non-polar analytes, with higher K(pw) and lower matrix effects than polydimethylsiloxane and polypropylene. Thus, a sorptive microextraction method, followed by large volume injection (LVI) gas chromatography-tandem mass spectrometry (GC-MS/MS), was proposed using the former sorbent (2 mg) for the simultaneous determination of model compounds in water samples. Good linearity (>0.99) was obtained for most of the analytes, except in the case of 4-nonylphenol (0.9466). Precision (n=4) at 50 and 500 ng L(-1) levels was in the 2-24% and limits of detection (LODs) were in the 0.6-25 ng L(-1) range for all the analytes studied. Copyright © 2011 Elsevier B.V. All rights reserved.

Effect of exposure routes on the relationships of lethal toxicity to rats from oral, intravenous, intraperitoneal and intramuscular routes.

PubMed

Ning, Zhong H; Long, Shuang; Zhou, Yuan Y; Peng, Zi Y; Sun, Yi N; Chen, Si W; Su, Li M; Zhao, Yuan H

2015-11-01

The lethal toxicity values (log 1/LD(50)) of 527 aliphatic and aromatic compounds in oral, intravenous, intramuscular and intraperitoneal routes were used to investigate the relationships of log 1/LD(50) from different exposure routes. Regression analysis shows that the log 1/LD(50) values are well correlated between intravenous and intraperitoneal or intramuscular injections. However, the correlations between oral and intravenous or intraperitoneal routes are relatively poor. Comparison of the average residuals indicates that intravenous injection is the most sensitive exposure route and oral administration is the least sensitive exposure route. This is attributed to the difference in kinetic process of toxicity testing. The toxic effect of a chemical can be similar or significantly different between exposure routes, depending on the absorption rates of chemicals into blood. Inclusion of hydrophobic parameter and fractions of ionic forms can improve the correlations between intravenous and intraperitoneal or oral routes, but not between intraperitoneal and oral routes. This is due to the differences of absorption rate in different exposure environments from different routes. Several factors, such as experimental uncertainty, metabolism and toxic kinetics, can affect the correlations between intravenous and intraperitoneal or oral routes. Copyright © 2015 Elsevier Inc. All rights reserved.

Multiple mitigation mechanisms: Effects of submerged plants on the toxicity of nine insecticides to aquatic animals.

PubMed

Brogan, William R; Relyea, Rick A

2017-01-01

Understanding the processes that regulate contaminant impacts in nature is an increasingly important challenge. For insecticides in surface waters, the ability of aquatic plants to sorb, or bind, hydrophobic compounds has been identified as a primary mechanism by which toxicity can be mitigated (i.e. the sorption-based model). However, recent research shows that submerged plants can also rapidly mitigate the toxicity of the less hydrophobic insecticide malathion via alkaline hydrolysis (i.e. the hydrolysis-based model) driven by increased water pH resulting from photosynthesis. However, it is still unknown how generalizable these mitigation mechanisms are across the wide variety of insecticides applied today, and whether any general rules can be ascertained about which types of chemicals may be mitigated by each mechanism. We quantified the degree to which the submerged plant Elodea canadensis mitigated acute (48-h) toxicity to Daphnia magna using nine commonly applied insecticides spanning three chemical classes (carbamates: aldicarb, carbaryl, carbofuran; organophosphates: malathion, diazinon, chlorpyrifos; pyrethroids: permethrin, bifenthrin, lambda-cyhalothrin). We found that insecticides possessing either high octanol-water partition coefficients (log K ow ) values (i.e. pyrethroids) or high susceptibility to alkaline hydrolysis (i.e. carbamates and malathion) were all mitigated to some degree by E. canadensis, while the plant had no effect on insecticides possessing intermediate log K ow values and low susceptibility to hydrolysis (i.e. chlorpyrifos and diazinon). Our results provide the first general insights into which types of insecticides are likely to be mitigated by different mechanisms based on known chemical properties. We suggest that current models and mitigation strategies would be improved by the consideration of both mitigation models. Copyright © 2016 Elsevier Ltd. All rights reserved.

Removal of pharmaceuticals, perfluoroalkyl substances and other micropollutants from wastewater using lignite, Xylit, sand, granular activated carbon (GAC) and GAC+Polonite® in column tests - Role of physicochemical properties.

PubMed

Rostvall, Ande; Zhang, Wen; Dürig, Wiebke; Renman, Gunno; Wiberg, Karin; Ahrens, Lutz; Gago-Ferrero, Pablo

2018-06-15

This study evaluated the performance of five different sorbents (granular activated carbon (GAC), GAC + Polonite ® (GAC + P), Xylit, lignite and sand) for a set of 83 micropollutants (MPs) (pharmaceuticals, perfluoroalkyl substances (PFASs), personal care products, artificial sweeteners, parabens, pesticide, stimulants), together representing a wide range of physicochemical properties. Treatment with GAC and GAC + P provided the highest removal efficiencies, with average values above 97%. Removal rates were generally lower for Xylit (on average 74%) and lignite (on average 68%), although they proved to be highly efficient for a few individual MPs. The average removal efficiency for sand was only 47%. It was observed that the MPs behaved differently depending on their physicochemical properties. The physicochemical properties of PFASs (i.e. molecular weight, topological molecular surface area, log octanol water partition coefficient (K ow ) and distribution coefficient between octanol and water (log D)) were positively correlated to observed removal efficiency for the sorbents Xylit, lignite and sand (p < 0.05), indicating a strong influence of perfluorocarbon chain length and associated hydrophobic characteristics. In contrast, for the other MPs the ratio between apolar and polar surface area (SA/SP) was positively correlated with the removal efficiency, indicating that hydrophobic adsorption may be a key feature of their sorption mechanisms. GAC showed to be the most promising filter medium to improve the removal of MPs in on-site sewage treatment facilities. However, more studies are needed to evaluate the removal of MPs in field trials. Copyright © 2018 Elsevier Ltd. All rights reserved.

Performance of combined fragmentation and retention prediction for the identification of organic micropollutants by LC-HRMS.

PubMed

Hu, Meng; Müller, Erik; Schymanski, Emma L; Ruttkies, Christoph; Schulze, Tobias; Brack, Werner; Krauss, Martin

2018-03-01

In nontarget screening, structure elucidation of small molecules from high resolution mass spectrometry (HRMS) data is challenging, particularly the selection of the most likely candidate structure among the many retrieved from compound databases. Several fragmentation and retention prediction methods have been developed to improve this candidate selection. In order to evaluate their performance, we compared two in silico fragmenters (MetFrag and CFM-ID) and two retention time prediction models (based on the chromatographic hydrophobicity index (CHI) and on log D). A set of 78 known organic micropollutants was analyzed by liquid chromatography coupled to a LTQ Orbitrap HRMS with electrospray ionization (ESI) in positive and negative mode using two fragmentation techniques with different collision energies. Both fragmenters (MetFrag and CFM-ID) performed well for most compounds, with average ranking the correct candidate structure within the top 25% and 22 to 37% for ESI+ and ESI- mode, respectively. The rank of the correct candidate structure slightly improved when MetFrag and CFM-ID were combined. For unknown compounds detected in both ESI+ and ESI-, generally positive mode mass spectra were better for further structure elucidation. Both retention prediction models performed reasonably well for more hydrophobic compounds but not for early eluting hydrophilic substances. The log D prediction showed a better accuracy than the CHI model. Although the two fragmentation prediction methods are more diagnostic and sensitive for candidate selection, the inclusion of retention prediction by calculating a consensus score with optimized weighting can improve the ranking of correct candidates as compared to the individual methods. Graphical abstract Consensus workflow for combining fragmentation and retention prediction in LC-HRMS-based micropollutant identification.

Effect of gamma irradiation on the microbiological quality and on the functional properties of proteins in dry red kidney beans ( Phaseolus vulgaris)

NASA Astrophysics Data System (ADS)

Dogbevi, M. K.; Vachon, C.; Lacroix, M.

2000-03-01

Gamma-irradiation was found to affect the physicochemical properties of dry red kidney beans. The highest dose used (8 kGy) significantly ( P⩽0.05) modified the extent of deamidation, the number of sulfhydryl groups, as well as the solubility and the hydrophobicity of the protein. Deamidation, protein solubility and hydrophobicity all increased with the irradiation dose while the number of sulfhydryl groups was reduced by the treatment. Furthermore, irradiation also affected the outgrowth of natural filamentous fungi contaminants present on the dry beans. A dose of 1.5 kGy reduced the number of filamentous fungi by 2 log cycles immediately after treatment. However, the highest dose used (3 kGy) did not eliminate the filamentous fungi completely. Moreover, the filamentous fungi population was a lot less diversified on the irradiated samples. Species of Aspergillus sp. and Penicillium sp. were more abundant on the unirradiated beans while the beans irradiated at 3 kGy contained were predominantly infected by species of Rhizopus sp. , Cladosporium sp. and Alternaria sp.

Ecological bioavailability of permethrin and p,p'-DDT: toxicity depends on type of organic matter resource.

PubMed

de Perre, Chloé; Trimble, Andrew J; Maul, Jonathan D; Lydy, Michael J

2014-02-01

Hydrophobic organic contaminants readily partition from aqueous to organic phases in aquatic systems with past research largely focusing on sediment. However, within many aquatic systems, matrices such as leaf material and detritus are abundant and ecologically important, as they may represent a primary exposure route for aquatic invertebrates. The objectives of the present study were to examine partitioning and toxicity to Hyalella azteca among permethrin and p,p'-DDT contaminated sediment, leaf, and a sediment-leaf mixture. Log organic carbon-water partitioning coefficients ranged from 4.21 to 5.82 for both insecticides, and were greatest within sediment and lowest in coarse leaf material. H. azteca lethal concentrations for 50% of the population (LC50s) ranged from 0.5 to 111μgg(-1) organic carbon, and were dependent on the matrix composition. The variation in sorption and toxicity among matrices common within stream ecosystems suggests that the ecological niche of aquatic organisms may be important for estimating risk of hydrophobic pesticides. Copyright © 2013 Elsevier Ltd. All rights reserved.

Lipase immobilized on the hydrophobic polytetrafluoroethene membrane with nonwoven fabric and its application in intensifying synthesis of butyl oleate.

PubMed

Wang, Shu-Guang; Zhang, Wei-Dong; Li, Zheng; Ren, Zhong-Qi; Liu, Hong-Xia

2010-11-01

The synthesis of butyl oleate was studied in this paper with immobilized lipase. Five types of membrane were used as support to immobilize Rhizopus arrhizus lipase by following a procedure combining filtration and protein cross-linking. Results showed that hydrophobic polytetrafluoroethene membrane with nonwoven fabric (HO-PTFE-NF) was the favorite choice in terms of higher protein loading, activity, and specific activity of immobilized lipase. The factors including solvent polarity, lipase dosage, concentration, and molar ratio of substrate and temperature were found to have significant influence on conversion. Results showed that hexane (logP = 3.53) was a favorable solvent for the biosynthesis of butyl oleate in our studies. The optimal conditions were experimentally determined of 50 U immobilized lipase, molar ratio of oleic acid to butanol of 1.0, substrate concentration of 0.12 mol/L, temperature of 37 °C, and reaction time of 2 h. The conversion was beyond 91% and decreased slightly after 18 cycles. Lipase immobilization can improve the conversion and the repeated use of immobilized lipase relative to free lipase.

Synergistic Effects of High Hydrostatic Pressure, Mild Heating, and Amino Acids on Germination and Inactivation of Clostridium sporogenes Spores

PubMed Central

Ishimori, Takateru; Takahashi, Katsutoshi; Goto, Masato; Nakagawa, Suguru; Kasai, Yoshiaki; Konagaya, Yukifumi; Batori, Hiroshi; Kobayashi, Atsushi

2012-01-01

The synergistic effects of high hydrostatic pressure (HHP), mild heating, and amino acids on the germination of Clostridium sporogenes spores were examined by determining the number of surviving spores that returned to vegetative growth after pasteurization following these treatments. Pressurization at 200 MPa at a temperature higher than 40°C and treatment with some of the 19 l-amino acids at 10 mM or higher synergistically facilitated germination. When one of these factors was omitted, the level of germination was insignificant. Pressures of 100 and 400 MPa were less effective than 200 MPa. The spores were effectively inactivated by between 1.8 and 4.8 logs by pasteurization at 80°C after pressurization at 200 MPa at 45°C for 120 min with one of the amino acids with moderate hydrophobicity, such as Leu, Phe, Cys Met, Ala, Gly, or Ser. However, other amino acids showed poor inactivation effects of less than 0.9 logs. Spores in solutions containing 80 mM of either Leu, Phe, Cys, Met, Ala, Gly, or Ser were successfully inactivated by pasteurization by more than 5.4 logs after pressurization at 200 MPa at 70°C for 15 to 120 min. Ala and Met reduced the spore viability by 2.8 and 1.8 logs, respectively, by pasteurization at a concentration of 1 mM under 200 MPa at 70°C. These results indicate that germination of the spores is facilitated by a combination of high hydrostatic pressure, mild heating, and amino acids. PMID:22983975

Structure of the frequency-interacting RNA helicase: a protein interaction hub for the circadian clock

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

Conrad, Karen S.; Hurley, Jennifer M.; Widom, Joanne

In the Neurospora crassa circadian clock, a protein complex of frequency (FRQ), casein kinase 1a (CK1a), and the FRQ-interacting RNA Helicase (FRH) rhythmically represses gene expression by the white-collar complex (WCC). FRH crystal structures in several conformations and bound to ADP/RNA reveal differences between FRH and the yeast homolog Mtr4 that clarify the distinct role of FRH in the clock. The FRQ-interacting region at the FRH N-terminus has variable structure in the absence of FRQ. A known mutation that disrupts circadian rhythms (R806H) resides in a positively charged surface of the KOW domain, far removed from the helicase core. Here,more » we show that changes to other similarly located residues modulate interactions with the WCC and FRQ. A V142G substitution near the N-terminus also alters FRQ and WCC binding to FRH, but produces an unusual short clock period. Finally, these data support the assertion that FRH helicase activity does not play an essential role in the clock, but rather FRH acts to mediate contacts among FRQ, CK1a and the WCC through interactions involving its N-terminus and KOW module.« less

Toxicity evaluation and prediction of toxic chemicals on activated sludge system.

PubMed

Cai, Bijing; Xie, Li; Yang, Dianhai; Arcangeli, Jean-Pierre

2010-05-15

The gaps of data for evaluating toxicity of new or overloaded organic chemicals on activated sludge system resulted in the requirements for methodology of toxicity estimation. In this study, 24 aromatic chemicals typically existed in the industrial wastewater were selected and classified into three groups of benzenes, phenols and anilines. Their toxicity on activated sludge was then investigated. Two indexes of IC(50-M) and IC(50-S) were determined respectively from the respiration rates of activated sludge with different toxicant concentration at mid-term (24h) and short-term (30min) time intervals. Experimental results showed that the group of benzenes was the most toxic, followed by the groups of phenols and anilines. The values of IC(50-M) of the tested chemicals were higher than those of IC(50-S). In addition, quantitative structure-activity relationships (QSARs) models developed from IC(50-M) were more stable and accurate than those of IC(50-S). The multiple linear models based on molecular descriptors and K(ow) presented better reliability than single linear models based on K(ow). Among these molecular descriptors, E(lumo) was the most important impact factor for evaluation of mid-term toxicity. Copyright (c) 2009 Elsevier B.V. All rights reserved.

Halogenated methyl-phenyl ethers (anisoles) in the environment: determination of vapor pressures, aqueous solubilities, Henry's law constants, and gas/water- (Kgw), n-octanol/water- (Kow) and gas/n-octanol (Kgo) partition coefficients.

PubMed

Pfeifer, O; Lohmann, U; Ballschmiter, K

2001-11-01

Halogenated methyl-phenyl ethers (methoxybenzenes, anisoles) are ubiquitous organics in the environment although they are not produced in industrial quantities. Modelling the fate of organic pollutants such as halogenated anisoles requires a knowledge of the fundamental physico-chemical properties of these compounds. The isomer-specific separation and detection of 60 of the 134 possible congeners allowing an environmental fingerprinting are reported in this study. The vapor pressure p0(L) of more than 60 and further physico-chemical properties of 26 available congeners are given. Vapor pressures p0(L), water solubilities S(L)W, and n-octanol/water partition coefficients Kow were determined by capillary HR-GC (High Resolution Gas Chromatography) on a non-polar phase and by RP-HPLC (Reversed Phase High Performance Liquid Chromatography) on a C18 phase with chlorobenzenes as reference standards. From these experimental data the Henry's law constants H, and the gas/water Kgw and gas/n-octanol Kgo partition coefficients were calculated. We found that vapor pressures, water solubilities, and n-octanol/water partition coefficients of the halogenated anisoles are close to those of the chlorobenzenes. A similar environmental fate of both groups can, therefore, be predicted.

Evaluation of virus removal efficiency of coagulation-sedimentation and rapid sand filtration processes in a drinking water treatment plant in Bangkok, Thailand.

PubMed

Asami, Tatsuya; Katayama, Hiroyuki; Torrey, Jason Robert; Visvanathan, Chettiyappan; Furumai, Hiroaki

2016-09-15

In order to properly assess and manage the risk of infection by enteric viruses in tap water, virus removal efficiency should be evaluated quantitatively for individual processes in actual drinking water treatment plants (DWTPs); however, there have been only a few studies due to technical difficulties in quantifying low virus concentration in water samples. In this study, the removal efficiency of indigenous viruses was evaluated for coagulation-sedimentation (CS) and rapid sand filtration (RSF) processes in a DWTP in Bangkok, Thailand by measuring the concentration of viruses before and after treatment processes using real-time polymerase chain reaction (qPCR). Water samples were collected and concentrated from raw source water, after CS, and after RSF, and inhibitory substances in water samples were reduced by use of a hydrophobic resin (DAX-8). Pepper mild mottle virus (PMMoV) and JC polyomavirus (JC PyV) were found to be highly prevalent in raw waters, with concentrations of 10(2.88 ± 0.35) and 10(3.06 ± 0.42) copies/L (geometric mean ± S.D.), respectively. Step-wise removal efficiencies were calculated for individual processes, with some variation observed between wet and dry seasons. During the wet season, PMMoV was removed less by CS and more by RSF on average (0.40 log10 vs 1.26 log10, respectively), while the reverse was true for JC PyV (1.91 log10 vs 0.49 log10, respectively). Both viruses were removed similarly during the dry season, with CS removing the most virus (PMMoV, 1.61 log10 and 0.78 log10; JC PyV, 1.70 log10, and 0.59 log10; CS and RSF, respectively). These differences between seasons were potentially due to variations in raw water quality and the characteristics of the viruses themselves. These results suggest that PMMoV and JC PyV, which are more prevalent in environmental waters than the other enteric viruses evaluated in this study, could be useful in determining viral fate for the risk management of viruses in water treatment processes in actual full-scale DWTPs. Copyright © 2016. Published by Elsevier Ltd.

Electrokinetic migration across artificial liquid membranes Tuning the membrane chemistry to different types of drug substances.

PubMed

Gjelstad, Astrid; Rasmussen, Knut Einar; Pedersen-Bjergaard, Stig

2006-08-18

Twenty different basic drugs were electrokinetically extracted across a thin artificial organic liquid membrane with a 300 V d.c. electrical potential difference as the driving force. From a 300 microl aqueous sample (acidified corresponding to 10mM HCl), the drugs were extracted for 5 min through a 200 microm artificial liquid membrane of a water immiscible organic solvent immobilized in the pores of a polypropylene hollow fiber, and into a 30 microl aqueous acceptor solution of 10mM HCl inside the lumen of the hollow fiber. Hydrophobic basic drugs (logP>1.7) were effectively isolated utilizing 2-nitrophenyl octyl ether (NPOE) as the artificial liquid membrane, with recoveries up to 83%. For more hydrophilic basic drugs (logP<1.0), a mixture of NPOE and 25% (w/w) di-(2-ethylhexyl) phosphate (DEHP) was required to ensure efficient extraction, resulting in recoveries up to 75%. DEHP was expected to act as an ion-pair reagent ion-pairing the protonated hydrophilic drugs at the interface between the sample and the membrane, resulting in permeation of the interface.

Demonstration/Validation of the Snap Sampler Passive Groundwater Sampling Device at the Former McClellan Air Force Base

DTIC Science & Technology

2011-02-01

and Development Center Fe Iron gpd Gallons per Day HDPE High Density Polyethylene Hg Mercury ICP Inductively Coupled Plasma ICP/MS...Inductively Coupled Plasma Mass Spectrometry IROD Interim Record of Decision ITRC Interstate Technology and Regulatory Council K Potassium Kow...alkaline earth metals, alkali metals, and a metalloid, were sampled. This particular demonstration took place at the McClellan Air Force Base (AFB) in

The Influence of Fluorocarbon and Hydrocarbon Acyl Groups at the Surface of Bovine Carbonic Anhydrase II on the Kinetics of Denaturation by Sodium Dodecyl Sulfate

PubMed Central

Lee, Andrew; Mirica, Katherine A.; Whitesides, George M.

2011-01-01

This paper examines the influence of acylation of the Lys-ε-NH3+ groups of bovine carbonic anhydrase (BCA, E.C. 4.2.1.1) to Lys-ε-NHCOR (R = -CH3, -CH2CH3, and -CH(CH3)2, -CF3) on the rate of denaturation of this protein in buffer containing sodium dodecyl sulfate (SDS). Analysis of the rates suggested separate effects due to electrostatic charge and hydrophobic interactions. Rates of denaturation (kAc,n) of each series of acylated derivatives depended on the number of acylations (n). Plots of log kAc,n vs. n followed U-shaped curves. Within each series of derivatives, rates of denaturation decreased as n increased to ~7; this decrease was compatible with increasingly unfavorable electrostatic interactions between SDS and protein. In this range of n, rates of denaturation also depended on the choice of the acyl group as n increased to ~7, in a manner compatible with favorable hydrophobic interactions between SDS and the -NHCOR groups. As n increased in the range 7 < n < 14 however, rates of denaturation stayed approximately constant; analysis suggested these rates were compatible with an increasingly important contribution to denaturation that depended both on the net negative charge of the protein and on the hydrophobicity of the R group. The mechanism of denaturation thus seems to change with the extent of acylation of the protein. For derivatives with the same net electrostatic charge, rates of denaturation increased with the acyl group (by a factor of ~3 for n ~ 14) in the order CH3CONH- < CH3CH2CONH- < (CH3)2CHCONH- < CF3CONH-. These results suggested that the hydrophobicity of CF3CONH- is slightly greater (by a factor of < 2) than that of RHCONH- similar in surface area. PMID:21182314

Influence of fluorocarbon and hydrocarbon acyl groups at the surface of bovine carbonic anhydrase II on the kinetics of denaturation by sodium dodecyl sulfate.

PubMed

Lee, Andrew; Mirica, Katherine A; Whitesides, George M

2011-02-10

This paper examines the influence of acylation of the Lys-ε-NH(3)(+) groups of bovine carbonic anhydrase (BCA, EC 4.2.1.1) to Lys-ε-NHCOR (R = -CH(3), -CH(2)CH(3), and -CH(CH(3))(2), -CF(3)) on the rate of denaturation of this protein in buffer containing sodium dodecyl sulfate (SDS). Analysis of the rates suggested separate effects due to electrostatic charge and hydrophobic interactions. Rates of denaturation (k(Ac,n)) of each series of acylated derivatives depended on the number of acylations (n). Plots of log k(Ac,n) vs n followed U-shaped curves. Within each series of derivatives, rates of denaturation decreased as n increased to ∼7; this decrease was compatible with increasingly unfavorable electrostatic interactions between SDS and protein. In this range of n, rates of denaturation also depended on the choice of the acyl group as n increased to ∼7, in a manner compatible with favorable hydrophobic interactions between SDS and the -NHCOR groups. As n increased in the range 7 < n < 14, however, rates of denaturation stayed approximately constant; analysis suggested that these rates were compatible with an increasingly important contribution to denaturation that depended both on the net negative charge of the protein and on the hydrophobicity of the R group. The mechanism of denaturation thus seems to change with the extent of acylation of the protein. For derivatives with the same net electrostatic charge, rates of denaturation increased with the acyl group (by a factor of ∼3 for n ∼ 14) in the order CH(3)CONH- < CH(3)CH(2)CONH- < (CH(3))(2)CHCONH- < CF(3)CONH-. These results suggested that the hydrophobicity of CF(3)CONH- is slightly greater (by a factor of <2) than that of RHCONH- with similar surface area.

CCQM-K104 key comparison (avermectin B1a) on the characterization of organic substances for chemical purity

NASA Astrophysics Data System (ADS)

Dai, Xinhua; Zhang, Wei; Li, Hongmei; Huang, Ting; Li, Mengwan; Quan, Can; Zhang, Qinghe; Davies, Stephen R.; Warren, John; Lo, Man-fung; Kakoulides, Elias; Ceyhan Gören, Ahmet; Marbumrung, Sornkrit; Pfeifer, Dietmar; Ün, İlker; Gündüz, Simay; Yilmaz, Hasibe; Kankaew, Pornhatai; Sudsiri, Nittaya; Shearman, Kittiya; Pookrod, Preeyaporn; Polzer, Joachim; Radeck, Wolfgang

2017-01-01

Under the Comité Consultatif pour la Quantité de Matière (CCQM), a key comparison, CCQM-K104, was coordinated by the National Institute of Metrology (NIM). The comparison was designed to demonstrate a laboratory's performance in determining the mass fraction of the main component in a complex high purity organic material. Nine NMIs or DIs participated in the comparison. Eight participants reported their results. An additional impurity was resolved from the avermectin B1a peak and was tentatively identified as an unknown impurity by NMIA (National Measurement Institute (Australia)). It was subsequently identified by NIM as a diastereoisomer of avermectin B1a at the C-26 position. Final reference value (KCRV) = 924.63 mg/g, with uncertainty (k=1) = 3.89 mg/g, and expanded uncertainty = 8.97 mg/g. The degrees of equivalence with the avermectin B1a KCRV for each participant were reported. The measurement results and degrees of equivalence should be indicative of the performance of a laboratory's measurement capability for the purity assignment of organic compounds of high structural complexity (relative molecular mass range of 500 Da -1000 Da and low polarity (-log KOW <= -2). Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Environmental risk assessment of hydrofluoroethers (HFEs).

PubMed

Tsai, Wen-Tien

2005-03-17

Hydrofluoroethers (HFEs) are being used as third generation replacements to chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs) and perfluorocarbons (PFCs) because of their nearly zero stratospheric ozone depletion and relatively low global warming potential. HFEs have been developed under commercial uses as cleaning solvents (incl., HFE-7500, C7F15OC2H5; HFE-7200, C4F9OC2H5; HFE-7100, C4F9CH3; HFE-7000, n-C3F7OCH3), blowing agents (incl., HFE-245mc, CF3CF2OCH3; HFC-356mec, CF3CHFCF2OCH3), refrigerants (incl., HFE-143a, CF3OCH3; HFE-134, CHF2OCHF2; HFE-245mc, CF3CF2OCH3), and dry etching agents in semiconductor manufacturing, (incl., HFE-227me, CF3OCHFCF3). From the environmental, ecological, and health points of view, it is important to understand their environmental risks for these HFEs from a diversity of commercial applications and industrial processes. This paper aims to introduce these HFEs with respect to physiochemical properties, commercial uses, and environmental hazards (i.e. global warming, photochemical potential, fire and explosion hazard, and environmental partition). Further, it addresses the updated data on the human toxicity, occupational exposure and potential health risk of commercial HFEs. It is concluded that there are few HFEs that still possess some environmental hazards, including global warming, flammability hazard and adverse effect of exposure. The partition coefficient for these HFEs has been estimated using the group contribution method; the values of logKow for commercial HFEs have been estimated to be below 3.5.

Rate of hydrolysis and degradation of the cyanogenic glycoside - dhurrin - in soil.

PubMed

Johansen, Henrik; Rasmussen, Lars Holm; Olsen, Carl Erik; Bruun Hansen, Hans Christian

2007-02-01

Cyanogenic glycosides are common plant toxins. Toxic hydrogen cyanide originating from cyanogenic glycosides may affect soil processes and water quality. In this study, hydrolysis, degradation and sorption of dhurrin (4-hydroxymandelonitrile-beta-d-glucoside) produced by sorghum has been studied in order to assess its fate in soil. The log K(ow) of dhurrin was -1.18+/-0.08 (22 degrees C). Hydrolysis was a first-order reaction with respect to dhurrin and hydroxyl ion concentrations. Half lives ranged from 1.2h (pH 8.6; 25 degrees C) to 530d (pH 4; 25 degrees C). The activation energy of hydrolysis was 112+9kJ. At pH 5.8 and room temperature, addition of humic acids (50gl(-1)) increased the rate of hydrolysis tenfold, while addition of kaolinite or goethite (100-250gl(-1)) both decreased the rate considerably. No significant sorption to soil components could be observed. The degradation rates of dhurrin in top and subsoils of Oxisols, Ultisols, Alfisols and Mollisols were studied at 22 degrees C (25mgl(-1), soil:liquid 1:1 (w:V), pH 3.8-8.1). Half-lives were 0.25-2h for topsoils, and 5-288h in subsoils. Hydrolysis in solution explained up to 45% of the degradation in subsoils whereas the contribution in topsoils was less than 14%, indicating the importance of enzymatic degradation processes. The highest risk of dhurrin leaching will take place when the soil is a low activity acid shallow soil with low content of clay minerals, iron oxides and humic acids.

Hazard evaluation of ten organophosphorous insecticides against the midge, Chironomus riparius via QSAR

USGS Publications Warehouse

Landrum, Peter F.; Fisher, Susan W.; Hwang, Haejo; Hickey, James P.

1999-01-01

Toxicities of ten organophosphorus (OP) insecticides were measured against midge larvae (Chironomus riparius) under varying temperature (11, 18, and 25°C) and pH (6, 7, and 8) conditions and with and without sediment. Toxicity usually increased with increasing temperature and was greater in the absence of sediment. No trend was found with varying pH. A series of unidimensional parameters and multidimensional models were used to describe the changes in toxicity. Log Kow was able to explain about 40–60% of the variability in response data for aqueous exposures while molecular volume and aqueous solubility were less predictive. Likewise, the linear solvation energy relationship (LSER) model only explained 40–70% of the response variability, suggesting that factors other than solubility were most important for producing the observed response. Molecular connectivity was the most useful for describing the variability in the response. In the absence of sediment, 1χv and 3κ were best able to describe the variation in response among all compounds at each pH (70–90%). In the presence of sediment, even molecular connectivity could not describe the variability until the partitioning potential to sediment was accounted for by assuming equilibrium partitioning. After correcting for partitioning, the same molecular connectivity terms as in the aqueous exposures described most of the variability, 61–87%, except for the 11°C data where correlations were not significant. Molecular connectivity was a better tool than LSER or the unidimensional variables to explain the steric fitness of OP insecticides which was crucial to the toxicity.

Very empirical treatment of solvation and entropy: a force field derived from Log Po/w

NASA Astrophysics Data System (ADS)

Kellogg, Glen Eugene; Burnett, James C.; Abraham, Donald J.

2001-04-01

A non-covalent interaction force field model derived from the partition coefficient of 1-octanol/water solubility is described. This model, HINT for Hydropathic INTeractions, is shown to include, in very empirical and approximate terms, all components of biomolecular associations, including hydrogen bonding, Coulombic interactions, hydrophobic interactions, entropy and solvation/desolvation. Particular emphasis is placed on: (1) demonstrating the relationship between the total empirical HINT score and free energy of association, ΔG interaction; (2) showing that the HINT hydrophobic-polar interaction sub-score represents the energy cost of desolvation upon binding for interacting biomolecules; and (3) a new methodology for treating constrained water molecules as discrete independent small ligands. An example calculation is reported for dihydrofolate reductase (DHFR) bound with methotrexate (MTX). In that case the observed very tight binding, ΔG interaction≤-13.6 kcal mol-1, is largely due to ten hydrogen bonds between the ligand and enzyme with estimated strength ranging between -0.4 and -2.3 kcal mol-1. Four water molecules bridging between DHFR and MTX contribute an additional -1.7 kcal mol-1 stability to the complex. The HINT estimate of the cost of desolvation is +13.9 kcal mol-1.

Dual functional nisin-multi-walled carbon nanotubes coated filters for bacterial capture and inactivation.

PubMed

Dong, Xiuli; Yang, Liju

2015-01-01

Removal of pathogens from water is one way to prevent waterborne illness. In this paper, we developed dual functional carbon nanotube (CNT) modified filters for bacterial capture and inactivation, utilizing multi-walled CNTs (MWCNTs) to coat on commercially available filters and making use of the exceptional adsorption property of CNTs to adsorb a natural antimicrobial peptide-nisin on it. Two types of MWCNTs with different outer layer diameters were used (MWCNTs1: <8 nm in diameter; MWCNTs2: 10-20 nm in diameter). The thickness of MWCNT layers, surface morphology, and surface hydrophobicity of both types of MWCNT coated filters were characterized. The MWCNT coating on filters significantly increased the surface hydrophobicity. The absorption of nisin and the capture of bacterial pathogens were correlated with increased surface hydrophobicity. The MWCNTs1 and MWCNTs2 filters with 1.5 mg MWCNTs loading captured 2.44 and 3.88 log of cells, respectively, from aqueous solutions containing a total of ~10(6) CFU/mL cells. Nisin deposit at the amount of 0.5 mg on the surfaces of MWCNT filters significantly reduced the viability of captured B. anthracis cells by 95.71-97.19 %, and inhibited the metabolic activities of the captured cells by approximately 98.3 %. The results demonstrated that the MWCNT-nisin filters achieved dual functions in bacterial pathogen capture and inhibition in one single filtration step, which is potentially applicable in removing undesired microorganisms from water sources and inhibiting captured Gram positive bacteria activities.

Trends and exceptions of physical properties on antibacterial activity for Gram-positive and Gram-negative pathogens.

PubMed

Brown, Dean G; May-Dracka, Tricia L; Gagnon, Moriah M; Tommasi, Ruben

2014-12-11

To better understand the difficulties surrounding the identification of novel antibacterial compounds from corporate screening collections, physical properties of ∼3200 antibacterial project compounds with whole cell activity against Gram-negative or Gram-positive pathogens were profiled and compared to actives found from high throughput (HTS) screens conducted on both biochemical and phenotypic bacterial targets. The output from 23 antibacterial HTS screens illustrated that when compared to the properties of the antibacterial project compounds, the HTS actives were significantly more hydrophobic than antibacterial project compounds (typically 2-4 log units higher), and furthermore, for 14/23 HTS screens, the average clogD was higher than the screening collection average (screening collection clogD = 2.45). It was found that the consequences of this were the following: (a) lead identification programs often further gained hydrophobic character with increased biochemical potency, making the separation even larger between the physicochemical properties of known antibacterial agents and the HTS active starting point, (b) the probability of plasma protein binding and cytotoxicity are often increased, and (c) cell-based activity in Gram-negative bacteria was severely limited or, if present, demonstrated significant efflux. Our analysis illustrated that compounds least susceptible to efflux were those which were highly polar and small in MW or very large and typically zwitterionic. Hydrophobicity was often the dominant driver for HTS actives but, more often than not, precluded whole cell antibacterial activity. However, simply designing polar compounds was not sufficient for antibacterial activity and pointed to a lack of understanding of complex and specific bacterial penetration mechanisms.

Sorption of perfluoroalkyl substances (PFASs) to an organic soil horizon - Effect of cation composition and pH.

PubMed

Campos Pereira, Hugo; Ullberg, Malin; Kleja, Dan Berggren; Gustafsson, Jon Petter; Ahrens, Lutz

2018-09-01

Accurate prediction of the sorption of perfluoroalkyl substances (PFASs) in soils is essential for environmental risk assessment. We investigated the effect of solution pH and calculated soil organic matter (SOM) net charge on the sorption of 14 PFASs onto an organic soil as a function of pH and added concentrations of Al 3+ , Ca 2+ and Na + . Often, the organic C-normalized partitioning coefficients (K OC ) showed a negative relationship to both pH (Δlog K OC /ΔpH = -0.32 ± 0.11 log units) and the SOM bulk net negative charge (Δlog K OC  = -1.41 ± 0.40 per log unit mol c g -1 ). Moreover, perfluorosulfonic acids (PFSAs) sorbed more strongly than perfluorocarboxylic acids (PFCAs) and the PFAS sorption increased with increasing perfluorocarbon chain length with 0.60 and 0.83 log K OC units per CF 2 moiety for C 3 -C 10 PFCAs and C 4 , C 6 , and C 8 PFSAs, respectively. The effects of cation treatment and SOM bulk net charge were evident for many PFASs with low to moderate sorption (C 5 -C 8 PFCAs and C 6 PFSA). However for the most strongly sorbing and most long-chained PFASs (C 9 -C 11 and C 13 PFCAs, C 8 PFSA and perfluorooctane sulfonamide (FOSA)), smaller effects of cations were seen, and instead sorption was more strongly related to the pH value. This suggests that the most long-chained PFASs, similar to other hydrophobic organic compounds, are preferentially sorbed to the highly condensed domains of the humin fraction, while shorter-chained PFASs are bound to a larger extent to humic and fulvic acid, where cation effects are significant. Copyright © 2018 The Authors. Published by Elsevier Ltd.. All rights reserved.

Proton transfer reaction mass spectrometry and time intensity perceptual measurement of flavor release from lipid emulsions using trained human subjects.

PubMed

Frank, Damian; Appelqvist, Ingrid; Piyasiri, Udayasika; Wooster, Tim J; Delahunty, Conor

2011-05-11

The effect of the fat component of liquid emulsions on dynamic "in-nose" flavor release was examined using a panel of trained human subjects (n = 6), proton transfer reaction mass spectrometry (PTR-MS), and time intensity (TI) sensory evaluation. A rigorous breathing and consumption protocol was developed, which synchronized subjects' breathing cycles and also the timing of sample introduction. Temporal changes in volatile release were measured in exhaled nostril breath by real-time PTR-MS. Corresponding changes in the perceived odor intensity could also be simultaneously measured using a push button TI device. The method facilitated accurate examination of both "preswallow" and "postswallow" phases of volatile release and perception. Volatile flavor compounds spanning a range of octanol/water partition coefficient (K(o/w)) values (1-1380) were spiked into water (0% fat) or lipid emulsions with various fat contents (2, 5, 10, and 20% fat). Replicate samples for each fat level were consumed according to the consumption protocol by six subjects. Statistical comparisons were made at the individual level and across the group for the effects of changes in the food matrix, such as fat content, on both pre- and postswallow volatile release. Significant group differences in volatile release parameters including area under the concentration curve (AUC) and maximum concentration (I(max)) were measured according to the lipid content of emulsions and volatile K(o/w). In a second experiment, using single compounds (2-heptanone, ethyl butanoate, and ethyl hexanoate), significant decreases in both in-nose volatile release and corresponding perceived odor intensities were measured with increasing fat addition. Overall, the effect of fat on in vivo release conformed to theory; fat had little effect on compounds with low K(o/w) values, but increased for volatiles with higher lipophilicity. In addition, significant pre- and postswallow differences were observed in AUC and I(max), as a result of changing fat levels. In the absence of fat, more than half of the total amount of volatile was released in the preswallow phase. As the content of fat was increased in the emulsion systems, the ratio of volatile released postswallow increased compared to preswallow. These data may provide new insights into why low-fat and high-fat foods are perceived differently.

Effects of polar and nonpolar groups on the solubility of organic compounds in soil organic matter

USGS Publications Warehouse

Chiou, C.T.; Kile, D.E.

1994-01-01

Vapor sorption capacities on a high-organic-content peat, a model for soil organic matter (SOM), were determined at room temperature for the following liquids: n-hexane, 1,4-dioxane, nitroethane, acetone, acetonitrile, 1-propanol, ethanol, and methanol. The linear organic vapor sorption is in keeping with the dominance of vapor partition in peat SOM. These data and similar results of carbon tetrachloride (CT), trichloroethylene (TCE), benzene, ethylene glycol monoethyl ether (EGME), and water on the same peat from earlier studies are used to evaluate the effect of polarity on the vapor partition in SOM. The extrapolated liquid solubility from the vapor isotherm increases sharply from 3-6 wt % for low-polarity liquids (hexane, CT, and benzene) to 62 wt % for polar methanol and correlates positively with the liquid's component solubility parameters for polar interaction (??P) and hydrogen bonding (??h). The same polarity effect may be expected to influence the relative solubilities of a variety of contaminants in SOM and, therefore, the relative deviations between the SOM-water partition coefficients (Kom) and corresponding octanol-water partition coefficients (Kow) for different classes of compounds. The large solubility disparity in SOM between polar and nonpolar solutes suggests that the accurate prediction of Kom from Kow or Sw (solute water solubility) would be limited to compounds of similar polarity.

Prediction of octanol-air partition coefficients for polychlorinated biphenyls (PCBs) using 3D-QSAR models.

PubMed

Chen, Ying; Cai, Xiaoyu; Jiang, Long; Li, Yu

2016-02-01

Based on the experimental data of octanol-air partition coefficients (KOA) for 19 polychlorinated biphenyl (PCB) congeners, two types of QSAR methods, comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA), are used to establish 3D-QSAR models using the structural parameters as independent variables and using logKOA values as the dependent variable with the Sybyl software to predict the KOA values of the remaining 190 PCB congeners. The whole data set (19 compounds) was divided into a training set (15 compounds) for model generation and a test set (4 compounds) for model validation. As a result, the cross-validation correlation coefficient (q(2)) obtained by the CoMFA and CoMSIA models (shuffled 12 times) was in the range of 0.825-0.969 (>0.5), the correlation coefficient (r(2)) obtained was in the range of 0.957-1.000 (>0.9), and the SEP (standard error of prediction) of test set was within the range of 0.070-0.617, indicating that the models were robust and predictive. Randomly selected from a set of models, CoMFA analysis revealed that the corresponding percentages of the variance explained by steric and electrostatic fields were 23.9% and 76.1%, respectively, while CoMSIA analysis by steric, electrostatic and hydrophobic fields were 0.6%, 92.6%, and 6.8%, respectively. The electrostatic field was determined as a primary factor governing the logKOA. The correlation analysis of the relationship between the number of Cl atoms and the average logKOA values of PCBs indicated that logKOA values gradually increased as the number of Cl atoms increased. Simultaneously, related studies on PCB detection in the Arctic and Antarctic areas revealed that higher logKOA values indicate a stronger PCB migration ability. From CoMFA and CoMSIA contour maps, logKOA decreased when substituents possessed electropositive groups at the 2-, 3-, 3'-, 5- and 6- positions, which could reduce the PCB migration ability. These results are expected to be beneficial in predicting logKOA values of PCB homologues and derivatives and in providing a theoretical foundation for further elucidation of the global migration behaviour of PCBs. Copyright © 2015 Elsevier Inc. All rights reserved.

Microincision Hydrophobic Acrylic Aspheric Toric Intraocular Lens for Astigmatism and Cataract Correction.

PubMed

Bissen-Miyajima, Hiroko; Negishi, Kazuno; Hieda, Osamu; Kinoshita, Shigeru

2015-06-01

To evaluate the efficacy and safety of a new acrylic one-piece toric intraocular lens (IOL). This prospective multicenter clinical trial included 93 eyes of 61 patients that were implanted with a hydrophobic acrylic toric IOL from 2010 to 2012 and followed for 1 year. This IOL uses the platform of a microincision one-piece aspheric IOL, the NY-60 IOL (HOYA, Tokyo, Japan), with three increments in cylindrical power (NHT15, 1.5 diopters [D]; NHT23, 2.25 D; and NHT30, 3.0 D). The inclusion criterion was preoperative corneal astigmatism from 0.75 to 3.00 D. The primary endpoint was uncorrected distance visual acuity (UDVA) of 0.0 logMAR (20/20 Snellen) or better 6 months postoperatively. In addition to UDVA, corrected distance visual acuity (CDVA), residual astigmatism, stability of the IOL alignment, need of realignment, and the rate of Nd:YAG laser capsulotomy were evaluated up to 1 year postoperatively. Errors in astigmatic correction were assessed using Alpin's vector analysis. The primary endpoint was achieved in 54.8% of eyes. One year postoperatively, the logMAR UDVAs were 0.02 ± 0.13, 0.05 ± 0.17, and 0.09 ± 0.14 with models NHT15, NHT23, and NHT30, which corresponds to 0.96 (19/20 Snellen), 0.89 (18/20 Snellen), and 0.82 (16/20 Snellen), respectively. One year postoperatively, the residual astigmatism was 0.66 ± 0.58 D. In each evaluation, the mean absolute change in the position of the axis mark was between 1.93° and 2.32°. Three eyes required repositioning of the IOL axis and 2 eyes received Nd:YAG laser capsulotomy. The correction error showed an undercorrection with against-the-rule astigmatism and overcorrection with with-the-rule astigmatism. The new one-piece toric IOL provided desirable clinical outcomes and stability in eyes with corneal astigmatism. Copyright 2015, SLACK Incorporated.

Emerging investigator series: development and application of polymeric electrospun nanofiber mats as equilibrium-passive sampler media for organic compounds.

PubMed

Qian, Jiajie; Jennings, Brandon; Cwiertny, David M; Martinez, Andres

2017-11-15

We fabricated a suite of polymeric electrospun nanofiber mats (ENMs) and investigated their performance as next-generation passive sampler media for environmental monitoring of organic compounds. Electrospinning of common polymers [e.g., polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), and polystyrene (PS), among others] yielded ENMs with reproducible control of nanofiber diameters (from 50 to 340 nm). The ENM performance was investigated initially with model hydrophilic (aniline and nitrobenzene) and hydrophobic (selected PCB congeners and dioxin) compounds, generally revealing fast chemical uptake into all of these ENMs, which was well described by a one compartment, first-order kinetic model. Typical times to reach 90% equilibrium (t 90% ) were ≤7 days under mixing conditions for all the ENMs and <0.5 days for the best performing materials under static (i.e., no mixing) conditions. Collectively, these short equilibrium timescales suggest that ENMs may be used in the field as an equilibrium-passive sampler, at least for our model compounds. Equilibrium partitioning coefficients (K ENM-W , L kg -1 ) averaged 2 and 4.7 log units for the hydrophilic and hydrophobic analytes, respectively. PAN, PMMA and PS were prioritized for additional studies because they exhibited not only the greatest capacity for simultaneous uptake of the entire model suite (log K ENM-W ∼1.5-6.2), but also fast uptake. For these optimized ENMs, the rates of uptake into PAN and PMMA were limited by aqueous phase diffusion to the nanofiber surface, and the rate-determining step for PS was analyte specific. Sorption isotherms also revealed that the environmental application of these optimized ENMs would occur within the linear uptake regime. We examined the ENM performance for the measurement of pore water concentrations from spiked soil and freshwater sediments. Soil and sediment studies not only yielded reproducible pore water concentrations and comparable values to other passive sampler materials, but also provided practical insights into ENM stability and fouling in such systems. Furthermore, fast uptake for a suite of structurally diverse hydrophilic and moderately hydrophobic compounds was obtained for PAN and PS, with t 90% ranging from 0.01 to 4 days with mixing and K ENM-W values ranging from 1.3 to 3.2 log units. Our findings show promise for the development and use of ENMs as equilibrium-passive samplers for a range of organic pollutants across soil/sediment and water systems.

Demonstration and Evaluation of Solid Phase Microextraction for the Assessment of Bioavailability and Contaminant Mobility

DTIC Science & Technology

2008-06-01

Toxicology and Chemistry, 8:499-512. Hansen, B.G., A.B. Paya-Perez, M. Rahman, and B.R. Larsen, QSARs for Kow and Koc of PCB Congeners: a Critical...Bioconcentration of Organic Chemicals in Earthworms (oligochaeta). Environmental Toxicology and Chemistry, 1998, 17, 2080-2090. Kraaij R, Mayer P. et al...Environmental Toxicology and Chemistry, 25, 11, 2869-2874 (2006). Lu, X.X., D.D Reible, J.W. Fleeger, ‘Adsorption/Desorption and Bioavailability

Demonstration of the AGI Universal Samplers (F.K.A. the GORE Modules) for Passive Sampling of Groundwater

DTIC Science & Technology

2014-03-27

Coefficient from Water into the Sorbent KOW Octanol-Water Partition Coefficient LF Low Flow LNAPL Light Non-aqueous Phase Liquid LTM Long-Term...Once in the vapor phase, the molecule can then diffuse through the mem- ERDC/CRREL TR-14-4 5 brane while liquid water is prevented from passing...remediation at this site was conducted in two phases. Phase I consisted of vertical contamina- tion profiling followed by the in situ injection of an

Demonstration of the AGI Universal Samplers (F.K.A. the GORE (registered trademark) Modules) for Passive Sampling of Groundwater

DTIC Science & Technology

2014-03-01

Coefficient from Water into the Sorbent KOW Octanol-Water Partition Coefficient LF Low Flow LNAPL Light Non-aqueous Phase Liquid LTM Long-Term...Once in the vapor phase, the molecule can then diffuse through the mem- ERDC/CRREL TR-14-4 5 brane while liquid water is prevented from passing...remediation at this site was conducted in two phases. Phase I consisted of vertical contamina- tion profiling followed by the in situ injection of an

Racemization of (S)-profen thioesters by strong neutral bases in nonpolar organic solvents: implication for ion-pair kinetic basicity.

PubMed

Chen, Chia-Yin; Chang, Yu-Shang; Lin, Shun-An; Wen, Hui-I; Cheng, Yu-Chi; Tsai, Shau-Wei

2002-05-17

The racemization of (S)-profen 2,2,2-trifluoroethyl thioesters in isooctane with trioctylamine as base was carried out, in which the Hammett equation log(k(int)) = 3.584sigma - 3.745 was successfully applied to describe the electron-withdrawing effect of the substituents to the alpha-phenyl moiety of the thioesters. A combination of neutral strong organic bases with different nonpolar solvents was employed to determine the second-order interconversion constants for the racemization of (S)-naproxen 2,2,2-trifluoroethyl thioester, in which solvent hydrophobicity was found to have less effect on the racemization. Implication for ion-pair kinetic basicity scale for the neutral strong bases in isooctane was further discussed.

Atom and receptor based 3D QSAR models for generating new conformations from pyrazolopyrimidine as IL-2 inducible tyrosine kinase inhibitors.

PubMed

Ul-Haq, Zaheer; Effendi, Juweria Shahrukh; Ashraf, Sajda; Bkhaitan, Majdi M

2017-06-01

In the current study, quantitative three-dimensional structure-activity-relationship (3D-QSAR) method was performed to design a model for new chemical entities by utilizing pyrazolopyrimidines. Their inhibiting activity on receptor IL-2 Itk correlates descriptors based on topology and hydrophobicity. The best model developed by ligand-based (atom-based) approach has correlation-coefficient of r 2 : 0.987 and cross-validated squared correlation-coefficient of q 2 : 0.541 with an external prediction capability of r 2 : 0.944. Whereas the best selected model developed by structured-based (receptor-based) approach has correlation-coefficient of r 2 : 0.987, cross-validated squared correlation-coefficient of q 2 : 0.637 with an external predictive ability of r 2 : 0.941. The statistical parameters prove that structure-based gave a better model to design new chemical scaffolds. The results achieved indicated that hydrophobicity at R 1 location play a vital role in the inhibitory activity and introduction of appropriately bulky and strongly hydrophobic-groups at position 3 of the terminal phenyl-group which is highly significant to enhance the activity. Six new pyrazolopyrimidine derivatives were designed. Docking simulation study was carried out and their inhibitory activity was predicted by the best structure based model with predictive activity of ranging from 8.43 to 8.85 log unit. The interacting residues PHE435, ASP500, LYS391, GLU436, MET438, CYS442, ILE369, VAL377 of PDB 4HCT were studied with respect to type of bonding with the new compounds. This study was aimed to search out more potent inhibitors of IL-2 Itk. Copyright © 2017 Elsevier Inc. All rights reserved.

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.

Alert-QSAR. Implications for Electrophilic Theory of Chemical Carcinogenesis

PubMed Central

Putz, Mihai V.; Ionaşcu, Cosmin; Putz, Ana-Maria; Ostafe, Vasile

2011-01-01

Given the modeling and predictive abilities of quantitative structure activity relationships (QSARs) for genotoxic carcinogens or mutagens that directly affect DNA, the present research investigates structural alert (SA) intermediate-predicted correlations ASA of electrophilic molecular structures with observed carcinogenic potencies in rats (observed activity, A = Log[1/TD50], i.e., ASA=f(X1SA,X2SA,…)). The present method includes calculation of the recently developed residual correlation of the structural alert models, i.e., ARASA=f(A−ASA,X1SA,X2SA,…). We propose a specific electrophilic ligand-receptor mechanism that combines electronegativity with chemical hardness-associated frontier principles, equality of ligand-reagent electronegativities and ligand maximum chemical hardness for highly diverse toxic molecules against specific receptors in rats. The observed carcinogenic activity is influenced by the induced SA-mutagenic intermediate effect, alongside Hansch indices such as hydrophobicity (LogP), polarizability (POL) and total energy (Etot), which account for molecular membrane diffusion, ionic deformation, and stericity, respectively. A possible QSAR mechanistic interpretation of mutagenicity as the first step in genotoxic carcinogenesis development is discussed using the structural alert chemoinformation and in full accordance with the Organization for Economic Co-operation and Development QSAR guidance principles. PMID:21954348

Effect of ionic liquid properties on lipase stabilization under microwave irradiation

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

Zhao, Hua; Baker, Gary A; Song, Zhiyan

2009-01-01

Ionic liquids (ILs) as neoteric solvents and microwave irradiation as alternative energy source are becoming two important tools for many enzymatic reactions. However, it is not well understood what properties of ILs govern the enzyme stabilization, and whether the microwave irradiation could activate enzymes in ILs. To tackle these two important issues, the synthetic activities of immobilized Candida antarctica lipase B (Novozyme 435) were examined in more than twenty ILs through microwave heating. Under microwave irradiation, enhanced enzyme activities were observed when the enzyme was surrounded by a layer of water molecules. However, such enhancement diminished when the reaction systemmore » was dried. To understand the effect of IL properties, the enzyme activities under microwave irradiation were correlated with the viscosity, polarity and hydrophobicity (log P) of ILs, respectively. The initial reaction rates bear no direct relationship with the viscosity and polarity (in terms of dielectric constant and EN T ) of ILs, but have a loose correlation (a bell curve) with log P values. The enzyme stabilization by ILs was explained from aspects of hydrogen-bond basicity of anions, dissolution of the enzyme, ionic association strength of anions, and substrate ground-state stabilization by ILs.« less

An advanced application of the quantitative structure-activity relationship concept in electrokinetic chromatography of metal complexes.

PubMed

Oszwałdowski, Sławomir; Timerbaev, Andrei R

2008-02-01

The relevance of the quantitative structure-activity relationship (QSAR) principle in MEKC and microemulsion EKC (MEEKC) of metal-ligand complexes was evaluated for a better understanding of analyte migration mechanism. A series of gallium chelates were applied as test solutes with available experimental migration data in order to reveal the molecular properties that govern the separation. The QSAR models operating with n-octanol-water partition coefficients or van der Waals volumes were found to be valid for estimation of the retention factors (log k') of neutral compounds when using only an aqueous MEEKC electrolyte. On the other hand, consistent approximations of log k' for both uncharged and charged complexes in either EKC mode (and also with hydro-organic BGEs) were achievable with two-parametric QSARs in which the dipole moment is additionally incorporated as a structural descriptor, reflecting the electrostatic solute-pseudostationary phase interaction. The theoretical analysis of significant molecular parameters in MEKC systems, in which the micellar BGE is modified with an organic solvent, confirmed that concomitant consideration of hydrophobic, electrostatic, and solvation factors is essential for explaining the migration behavior of neutral metal complexes.

Influence of natural organic matter on equilibrium adsorption of neutral and charged pharmaceuticals onto activated carbon.

PubMed

de Ridder, D J; Verliefde, A R D; Heijman, S G J; Verberk, J Q J C; Rietveld, L C; van der Aa, L T J; Amy, G L; van Dijk, J C

2011-01-01

Natural organic matter (NOM) can influence pharmaceutical adsorption onto granular activated carbon (GAC) by direct adsorption competition and pore blocking. However, in the literature there is limited information on which of these mechanisms is more important and how this is related to NOM and pharmaceutical properties. Adsorption batch experiments were carried out in ultrapure, waste- and surface water and fresh and NOM preloaded GAC was used. Twenty-one pharmaceuticals were selected with varying hydrophobicity and with neutral, negative or positive charge. The influence of NOM competition and pore blocking could not be separated. However, while reduction in surface area was similar for both preloaded GACs, up to 50% lower pharmaceutical removal was observed on wastewater preloaded GAC. This was attributed to higher hydrophobicity of wastewater NOM, indicating that NOM competition may influence pharmaceutical removal more than pore blocking. Preloaded GAC was negatively charged, which influenced removal of charged pharmaceuticals significantly. At a GAC dose of 6.7 mg/L, negatively charged pharmaceuticals were removed for 0-58%, while removal of positively charged pharmaceuticals was between 32-98%. Charge effects were more pronounced in ultrapure water, as it contained no ions to shield the surface charge. Solutes with higher log D could compete better with NOM, resulting in higher removal.

Unraveling the Relative Importance of Oral and Dermal Contaminant Exposure in Reptiles: Insights from Studies Using the Western Fence Lizard (Sceloporus occidentalis)

PubMed Central

Weir, Scott M.; Talent, Larry G.; Anderson, Todd A.; Salice, Christopher J.

2014-01-01

Despite widespread recognition of significant data deficiencies, reptiles remain a relatively understudied taxon in ecotoxicology. To conduct ecological risk assessments on reptiles frequently requires using surrogate taxa such as birds, but recent research suggests that reptiles have significantly different exposure profiles and toxicant sensitivity. We exposed western fence lizards, Sceloporus occidentalis, to the same quantities of three model chemicals via oral (gavage) and dermal (ventral skin application) exposure for either 24 or 48 hours. Three phthalate esters (di-methyl phthalate [DMP], di-iso-butyl phthalate [DIBP], and di-n-octyl phthalate [DNOP]) were chosen as model chemicals because they represent a gradient of lipophilicity but are otherwise structurally similar. Overall, the more lipophilic phthalates (DIBP and DNOP) were found to have higher concentrations in tissues than the less lipophilic DMP. Significant differences in tissue concentrations between DIBP and DNOP were tissue-dependent, suggesting that delivery to a site of action following exposure is not only a simple function of lipophilicity. In dermal treatments, DMP usually had fewer detections (except in ventral skin samples), suggesting that lipophilicity (log Kow>2) is a requirement for uptake across the skin. In general, tissue residues were greater in oral treatments than dermal treatments (significant in adipose and liver tissue), but differences were driven strongly by differences in DMP which did not appear to be absorbed well across skin. When differences in tissue residue concentrations between oral and dermal exposure did occur, the difference was not drastic. Taken together these results suggest that dermal exposure should be considered in risk assessments for reptilian receptors. Dermal exposure may be an especially important route for reptiles as their ectothermic physiology translates to lower energetic demands and dietary exposure compared to birds and mammals. PMID:24941063

How efficient are constructed wetlands in removing pharmaceuticals from untreated and treated urban wastewaters? A review.

PubMed

Verlicchi, Paola; Zambello, Elena

2014-02-01

This review presents and discusses the data from 47 peer-reviewed journal articles on the occurrence of 137 pharmaceutical compounds in the effluent from various types of constructed wetlands treating urban wastewater. We analyse the observed removal efficiencies of the investigated compounds in order to identify the type of constructed wetland that best removes those most frequently detected. The literature reviewed details experimental investigations carried out on 136 treatment plants, including free water surface systems, as well as horizontal and vertical subsurface flow beds (pilot or full-scale) acting as primary, secondary or tertiary treatments. The occurrence of selected pharmaceuticals in sediments and gravel and their uptake by common macrophytes are also presented and discussed. We analyse the main removal mechanisms for the selected compounds and investigate the influence of the main design parameters, as well as operational and environmental conditions of the treatment systems on removal efficiency. We also report on previous attempts to correlate observed removal values with the chemical structure and chemical-physical properties (mainly pKa and LogKow) of pharmaceutical compounds. We then use the literature data to calculate the average pharmaceutical mass loadings in the effluent from constructed wetlands, comparing the ability of such systems to remove selected pharmaceuticals with the corresponding conventional secondary and tertiary treatments. Finally, the environmental risk posed by pharmaceutical residues in effluents from constructed wetlands acting as secondary and tertiary treatment steps is calculated in the form of the risk quotient ratio. This approach enabled us to provide a ranking of the most critical compounds for the two scenarios, to discuss the ramifications of the adoption of constructed wetlands for removing such persistent organic compounds, and to propose avenues of future research. © 2013.

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.

Diclofenac in municipal wastewater treatment plant: quantification using laser diode thermal desorption--atmospheric pressure chemical ionization--tandem mass spectrometry approach in comparison with an established liquid chromatography-electrospray ionization-tandem mass spectrometry method.

PubMed

Lonappan, Linson; Pulicharla, Rama; Rouissi, Tarek; Brar, Satinder K; Verma, Mausam; Surampalli, Rao Y; Valero, José R

2016-02-12

Diclofenac (DCF), a prevalent non-steroidal anti-inflammatory drug (NSAID) is often detected in wastewater and surface water. Analysis of the pharmaceuticals in complex matrices is often laden with challenges. In this study a reliable, rapid and sensitive method based on laser diode thermal desorption/atmospheric pressure chemical ionization (LDTD/APCI) coupled with tandem mass spectrometry (MS/MS) has been developed for the quantification of DCF in wastewater and wastewater sludge. An established conventional LC-ESI-MS/MS (liquid chromatography-electrospray ionization-tandem mass spectrometry) method was compared with LDTD-APCI-MS/MS approach. The newly developed LDTD-APCI-MS/MS method reduced the analysis time to 12s in lieu of 12 min for LC-ESI-MS/MS method. The method detection limits for LDTD-APCI-MS/MS method were found to be 270 ng L(-1) (LOD) and 1000 ng L(-1) (LOQ). Furthermore, two extraction procedures, ultrasonic assisted extraction (USE) and accelerated solvent extraction (ASE) for the extraction of DCF from wastewater sludge were compared and ASE with 95.6 ± 7% recovery was effective over USE with 86 ± 4% recovery. The fate and partitioning of DCF in wastewater (WW) and wastewater sludge (WWS) in wastewater treatment plant was also monitored at various stages of treatment in Quebec Urban community wastewater treatment plant. DCF exhibited affinity towards WW than WWS with a presence about 60% of DCF in WW in contrary with theoretical prediction (LogKow=4.51). Copyright © 2016 Elsevier B.V. All rights reserved.

Carbamazepine and naproxen: fate in wetland mesocosms planted with Scirpus validus.

PubMed

Zhang, Dong Qing; Hua, Tao; Gersberg, Richard M; Zhu, Junfei; Ng, Wun Jern; Tan, Soon Keat

2013-03-01

Scirpus validus was grown hydroponically and exposed to the pharmaceuticals, carbamazepine and naproxen at concentrations of 0.5-2.0 mg L(-1) for an exposure duration of up to 21 d. By the end of experiment, carbamazepine elimination from the nutrient solution reached to 74%, while nearly complete removal (>98%) was observed for naproxen. Photodegradation and biodegradation played only minor roles for carbamazepine elimination, while naproxen showed a high potential for both photodegradation and biodegradation. Levels of carbamazepine ranged from 3.3 to19.0 μg g(-1) (fresh weight) in the roots and 0.3-0.7 μg g(-1) (fresh weight) in the shoots, while naproxen concentrations were 0.2-2.4 μg g(-1) (fresh weight) in the roots and 0.2-2.8 μg g(-1) (fresh weight) in the shoots. Bioaccumulation factors (BAFs) for carbamazepine ranged from 5.5 to 13.0 for roots and 0.3-1.0 for shoots, and uptake by S. validus accounted for up to 22% of the total mass loss of carbamazepine in the nutrient solutions. All BAFs for naproxen were less than 4.2 and plant uptake accounted for less than 5% of the total mass loss of naproxen, implying that plant uptake was not significant in naproxen elimination. The rather limited plant uptake of naproxen was not surprising despite the fact that its log K(ow) is close to the optimal range (1.8-3.1) for maximal potential for plant uptake. Apparently, for ionizable compounds such as naproxen, the effects of pK(a) and pH partitioning might be more important than lipophilicity. Copyright © 2012 Elsevier Ltd. All rights reserved.

Validation of a GC-MS/MS method for simultaneous determination of 86 persistent organic pollutants in marine sediments by pressurized liquid extraction followed by stir bar sorptive extraction.

PubMed

Camino-Sánchez, F J; Zafra-Gómez, Alberto; Pérez-Trujillo, J P; Conde-González, J E; Marques, J C; Vílchez, José Luis

2011-08-01

A multiresidue method for the analysis of 86 persistent pollutants in marine sediments at ultra-trace level has been developed and validated using pressurized liquid extraction (PLE) and stir-bar sorptive extraction (SBSE) coupled with thermal desorption and gas chromatography-triple quadrupole mass spectrometry (TD-GC-MS/MS QqQ). The compounds analyzed belong to various families such as polychlorinated biphenyls, polycyclic aromatic hydrocarbons, polybrominated diphenylethers, organophosphorus and organochlorine pesticides and other pesticides such as urons, and triazines. The analytes have very different polarities and log K(ow) values, which is an important parameter in the optimization of a SBSE method. Due to PLE high efficiency and throughput rates, along with the proven ability for multiresidue analysis and excellent sensitivity of SBSE, we present an efficient method. The limits of quantification obtained ranged from 0.014 to 1.0 ng g(-1), with detection limits below pg g(-1) levels. In order to validate the proposed methodology, quality parameters such as recovery, linearity and reproducibility were studied. Recoveries ranged from 63% to 119%, reproducibility (in terms of Relative Standard Deviation for ten determinations) was lower than 35% in all cases, and determination coefficients higher than 0.990 for all analytes. The main factors that affect PLE, SBSE and GC-MS/MS procedures were optimized. The method was applied to the analysis of nine marine sediments obtained from the nine main submarine wastewater discharge points (emissaries) presents along the coast of Tenerife Island (Canary Islands, Spain). Copyright © 2011 Elsevier Ltd. All rights reserved.

Unraveling the relative importance of oral and dermal contaminant exposure in reptiles: insights from studies using the western fence lizard (Sceloporus occidentalis).

PubMed

Weir, Scott M; Talent, Larry G; Anderson, Todd A; Salice, Christopher J

2014-01-01

Despite widespread recognition of significant data deficiencies, reptiles remain a relatively understudied taxon in ecotoxicology. To conduct ecological risk assessments on reptiles frequently requires using surrogate taxa such as birds, but recent research suggests that reptiles have significantly different exposure profiles and toxicant sensitivity. We exposed western fence lizards, Sceloporus occidentalis, to the same quantities of three model chemicals via oral (gavage) and dermal (ventral skin application) exposure for either 24 or 48 hours. Three phthalate esters (di-methyl phthalate [DMP], di-iso-butyl phthalate [DIBP], and di-n-octyl phthalate [DNOP]) were chosen as model chemicals because they represent a gradient of lipophilicity but are otherwise structurally similar. Overall, the more lipophilic phthalates (DIBP and DNOP) were found to have higher concentrations in tissues than the less lipophilic DMP. Significant differences in tissue concentrations between DIBP and DNOP were tissue-dependent, suggesting that delivery to a site of action following exposure is not only a simple function of lipophilicity. In dermal treatments, DMP usually had fewer detections (except in ventral skin samples), suggesting that lipophilicity (log Kow>2) is a requirement for uptake across the skin. In general, tissue residues were greater in oral treatments than dermal treatments (significant in adipose and liver tissue), but differences were driven strongly by differences in DMP which did not appear to be absorbed well across skin. When differences in tissue residue concentrations between oral and dermal exposure did occur, the difference was not drastic. Taken together these results suggest that dermal exposure should be considered in risk assessments for reptilian receptors. Dermal exposure may be an especially important route for reptiles as their ectothermic physiology translates to lower energetic demands and dietary exposure compared to birds and mammals.

Bioaccumulation of polycyclic aromatic compounds: 1. Bioconcentration in two marine species and in semipermeable membrane devices during chronic exposure to dispersed crude oil.

PubMed

Baussant, T; Sanni, S; Jonsson, G; Skadsheim, A; Børseth, J F

2001-06-01

Assessing the fate in marine biota of hydrocarbons derived from oil particles that are discharged during exploration and production is of relevant environmental concern. However, a rather complex experimental setup is required to carry out such investigations. In this study, a sophisticated tool, the continuous-flow system (CFS), was used to mimic dispersed oil exposure to marine biota. Polycyclic aromatic hydrocarbon (PAH) uptake was studied in two species, the blue mussel Mytilus edulis and juvenile of the turbot Scophthalmus maximus, and in semipermeable membrane devices (SPMD) exposed to crude oil dispersed in a flow-through system. After an exposure period of 8 to 21 d, elimination in organisms and devices was analyzed for 9 to 10 d following transfer to PAH-free seawater. Principal component analysis (PCA) revealed different PAH patterns. In mussel and SPMD, the PAH profiles were very close to that analyzed in seawater. Slight differences were, however, indicated for large molecules with log Kow above six. Nonachievement of steady-state concentration and bioavailability of PAH in oil droplets may account for these differences. The PAH composition in fish revealed only congeners with two to three aromatic rings. A combination of bioavailability and efficient metabolism of the larger PAH molecules may explain this pattern. The CFS made possible a better understanding of some critical factors governing bioconcentration in marine biota from dispersed oil. Yet the results illustrate that uptake of PAH from exposure to oil particles is complex and that different species may bioconcentrate different molecules depending on factors like life style and metabolic capability to degrade the potential harmful substances. Hence, risk assessment of the actual impact of discharges to marine biota should consider these essential biological and ecological factors.

Current status and historical trends of organochlorine pesticides in the ecosystem of Deep Bay, South China

NASA Astrophysics Data System (ADS)

Qiu, Yao-Wen; Zhang, Gan; Guo, Ling-Li; Cheng, Hai-Rong; Wang, Wen-Xiong; Li, Xiang-Dong; Wai, Onyx W. H.

2009-11-01

To characterize the current status and historical trends in organochlorine pesticides (OCPs) contamination in Deep Bay, an important water body between Hong Kong and mainland China with a Ramsar mangrove wetland (Maipo), samples from seawater, suspended particulate matter (SPM), surface sediment, sediment core and fish were collected to determine the OCPs concentrations. Sediment core dating was accomplished using the 210Pb method. The average concentrations of DDTs, HCHs and chlordanes in water were 1.96, 0.71, 0.81 ng l -1, while in SPM were 36.5, 2.5, 35.7 ng g -1 dry weight, in surface sediment were 20.2, 0.50, 2.4 ng g -1 dry weight, and in fish were 125.4, 0.43, 13.1 ng g -1 wet weight, respectively. DDTs concentrations in various matrices of Deep Bay were intermediate compared with those in other areas. Temporal trends of the targeted OCPs levels in sediment core generally increased from 1948 to 2004, with the highest levels in top or sub-surface sediment. Both DDT composition and historical trends indicated an ongoing fresh DDT input. A positive relationship between the bioconcentration factor (BCF) of target chemicals and the corresponding octanol-water partition coefficient ( Kow), and between the biota-sediment accumulation factors (BSAF) and the Kow were observed in the Bay. The risk assessment indicated that there were potential ecological and human health risks for the target OCPs in Deep Bay.

Calculation of Physicochemical Properties for Short- and Medium-Chain Chlorinated Paraffins

NASA Astrophysics Data System (ADS)

Glüge, Juliane; Bogdal, Christian; Scheringer, Martin; Buser, Andreas M.; Hungerbühler, Konrad

2013-06-01

Short- and medium-chain chlorinated paraffins are potential PBT chemicals (persistent, bioaccumulative, toxic) and short-chain chlorinated paraffins are under review for inclusion in the UNEP Stockholm Convention on Persistent Organic Pollutants. Despite their high production volume of more than one million metric tonnes per year, only few data on their physicochemical properties are available. We calculated subcooled-liquid vapor pressure, subcooled-liquid solubility in water and octanol, Henry's law constant for water and octanol, as well as the octanol-water partition coefficient with the property calculation methods COSMOtherm, SPARC, and EPI Suite™, and compared the results to experimental data from the literature. For all properties, good or very good agreement between calculated and measured data was obtained for COSMOtherm; results from SPARC were in good agreement with the measured data except for subcooled-liquid water solubility, whereas EPI Suite™ showed the largest discrepancies for all properties. After critical evaluation of the three property calculation methods, a final set of recommended property data for short- and medium-chain chlorinated paraffins was derived. The calculated property data show interesting relationships with chlorine content and carbon chain length. Increasing chlorine content does not cause pronounced changes in water solubility and octanol-water partition coefficient (KOW) as long as it is below 55%. Increasing carbon chain length leads to strong increases in KOW and corresponding decreases in subcooled-liquid water solubility. The present data set can be used in further studies to assess the environmental fate and human exposure of this relevant compound class.

Polycyclic aromatic hydrocarbons (PAHs) in the water column and sediment core of Deep Bay, South China

NASA Astrophysics Data System (ADS)

Qiu, Yao-Wen; Zhang, Gan; Liu, Guo-Qing; Guo, Ling-Li; Li, Xiang-Dong; Wai, Onyx

2009-06-01

The levels of 15 polycyclic aromatic hydrocarbons (PAHs) were determined in seawater, suspended particulate matter (SPM), surface sediment and core sediment samples of Deep Bay, South China. The average concentrations Σ 15PAHs were 69.4 ± 24.7 ng l -1 in seawater, 429.1 ± 231.8 ng g -1 in SPM, and 353.8 ± 128.1 ng g -1 dry weight in surface sediment, respectively. Higher PAH concentrations were observed in SPM than in surface sediment. Temporal trend of PAH concentrations in core sediment generally increased from 1948 to 2004, with higher concentrations in top than in sub-surface, implying a stronger recent input of PAHs owing to the rapid economic development in Shenzhen. Compared with historical data, the PAH levels in surface sediment has increased, and this was further confirmed by the increasing trend of PAHs in the core sediment. Phenanthrene, fluoranthene and pyrene dominated in the PAH composition pattern profiles in the Bay. Compositional pattern analysis suggested that PAHs in the Deep Bay were derived from both pyrogenic and petrogenic sources, and diesel oil leakage, river runoff and air deposition may serve as important pathways for PAHs input to the Bay. Significant positive correlations between partition coefficient in surface sediment to that in water ( KOC) of PAH and their octanol/water partition coefficients ( KOW) were observed, suggesting that KOC of PAHs in sediment/water of Deep Bay may be predicted by the corresponding KOW.

Parameterization models for pesticide exposure via crop consumption.

PubMed

Fantke, Peter; Wieland, Peter; Juraske, Ronnie; Shaddick, Gavin; Itoiz, Eva Sevigné; Friedrich, Rainer; Jolliet, Olivier

2012-12-04

An approach for estimating human exposure to pesticides via consumption of six important food crops is presented that can be used to extend multimedia models applied in health risk and life cycle impact assessment. We first assessed the variation of model output (pesticide residues per kg applied) as a function of model input variables (substance, crop, and environmental properties) including their possible correlations using matrix algebra. We identified five key parameters responsible for between 80% and 93% of the variation in pesticide residues, namely time between substance application and crop harvest, degradation half-lives in crops and on crop surfaces, overall residence times in soil, and substance molecular weight. Partition coefficients also play an important role for fruit trees and tomato (Kow), potato (Koc), and lettuce (Kaw, Kow). Focusing on these parameters, we develop crop-specific models by parametrizing a complex fate and exposure assessment framework. The parametric models thereby reflect the framework's physical and chemical mechanisms and predict pesticide residues in harvest using linear combinations of crop, crop surface, and soil compartments. Parametric model results correspond well with results from the complex framework for 1540 substance-crop combinations with total deviations between a factor 4 (potato) and a factor 66 (lettuce). Predicted residues also correspond well with experimental data previously used to evaluate the complex framework. Pesticide mass in harvest can finally be combined with reduction factors accounting for food processing to estimate human exposure from crop consumption. All parametric models can be easily implemented into existing assessment frameworks.

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.

Rapid-gradient HPLC method for measuring drug interactions with immobilized artificial membrane: comparison with other lipophilicity measures.

PubMed

Valko, K; Du, C M; Bevan, C D; Reynolds, D P; Abraham, M H

2000-08-01

A fast-gradient high-performance liquid chromatographic (HPLC) method has been suggested to characterize the interactions of drugs with an immobilized artificial membrane (IAM). With a set of standards, the gradient retention times can be converted to Chromatographic Hydrophobicity Index values referring to IAM chromatography (CHI(IAM)) that approximates an acetonitrile concentration with which the equal distribution of compound can be achieved between the mobile phase and IAM. The CHI(IAM) values are more suitable for interlaboratory comparison and for high throughput screening of new molecular entities than the log k(IAM) values (isocratic retention factor on IAM). The fast-gradient method has been validated against the isocratic log k(IAM) values using the linear free energy relationship solvation equations based on the data from 48 compounds. The compound set was selected to provide a wide range and the least cross-correlation between the molecular descriptors in the solvation equation: (2) where SP is a solute property (e.g., logarithm of partition coefficients, reversed-phase (RP)-HPLC retention parameters, such as log k, log k(w), etc.) and the explanatory variables are solute descriptors as follows: R(2) is an excess molar refraction that can be obtained from the measured refractive index of a compound, pi(2)(H) is the solute dipolarity/polarizability, summation operatoralpha(2)(H) and summation operatorbeta(2)(0) are the solute overall or effective hydrogen-bond acidity and basicity, respectively, and V(x) is the McGowan characteristic volume (in cm(3)/100 mol) that can be calculated for any solute simply from molecular structure using a table of atomic constants. It was found that the relative constants of the solvation equation were very similar for the CHI(IAM) and for the log k(IAM). The IAM lipophilicity scale was quite similar to the octanol/water lipophilicity scale for neutral compounds. The effect of charge on the interaction with IAM was studied by varying the mobile phase pH. Copyright 2000 Wiley-Liss, Inc.

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.

Consecutive case series of 244 age-related macular degeneration patients undergoing implantation with an extended macular vision IOL.

PubMed

Qureshi, Muhammad A; Robbie, Scott J; Hengerer, Fritz H; Auffarth, Gerd U; Conrad-Hengerer, Ina; Artal, Pablo

2018-03-01

To determine safety and visual outcomes in eyes with age-related macular degeneration (AMD) implanted with a novel intraocular lens (IOL) that delivers an optimized retinal image to all macular areas within 10 degrees of retinal eccentricity. This was a consecutive case series of 244 eyes with dry/stable wet AMD and logMAR visual acuity ≥0.3 implanted with iolAMD Eyemax mono TM (London Eye Hospital Pharma), a single-piece, injectable, hydrophobic acrylic IOL sited in the capsular bag. Primary outcome was safety. Secondary outcomes were changes in corrected distance visual acuity (CDVA) and corrected near visual acuity (CNVA) (logMAR). Mean age at surgery was 80 years. Mean duration of follow-up was 3 months (range 1-16 months). No eyes had worsening of CDVA. Frequency of perioperative complications was equivalent to standard IOL implantation. Postoperative refractive outcomes were within ±1 D of the target refraction in 88% of cases. Mean preoperative CDVA improved from 1.06 to 0.71 postoperatively (mean of differences -0.35; 95% confidence interval [CI] -0.3886 to -0.3223; p<0.0001), equating to an approximate Early Treatment Diabetic Retinopathy Study gain of 18 letters. Mean preoperative CNVA (N-point; logMAR conversion) improved from 1.36 to 0.88 postoperatively (mean of differences -0.48; 95% CI -0.53 to -0.44; p<0.0001). This novel IOL appears safe in the short to medium term. Improvements in postoperative CDVA and CNVA exceed those observed with standard implants.

Spatial organization of surface nanobubbles and its implications in their formation process.

PubMed

Lhuissier, Henri; Lohse, Detlef; Zhang, Xuehua

2014-02-21

We study the size and spatial distribution of surface nanobubbles formed by the solvent exchange method to gain insight into the mechanism of their formation. The analysis of Atomic Force Microscopy (AFM) images of nanobubbles formed on a hydrophobic surface reveals that the nanobubbles are not randomly located, which we attribute to the role of the history of nucleation during the formation. Moreover, the size of each nanobubble is found to be strongly correlated with the area of the bubble-depleted zone around it. The precise correlation suggests that the nanobubbles grow by diffusion of the gas from the bulk rather than by diffusion of the gas adsorbed on the surface. Lastly, the size distribution of the nanobubbles is found to be well described by a log-normal distribution.

Kinetics of hydrogen peroxide decomposition by catalase: hydroxylic solvent effects.

PubMed

Raducan, Adina; Cantemir, Anca Ruxandra; Puiu, Mihaela; Oancea, Dumitru

2012-11-01

The effect of water-alcohol (methanol, ethanol, propan-1-ol, propan-2-ol, ethane-1,2-diol and propane-1,2,3-triol) binary mixtures on the kinetics of hydrogen peroxide decomposition in the presence of bovine liver catalase is investigated. In all solvents, the activity of catalase is smaller than in water. The results are discussed on the basis of a simple kinetic model. The kinetic constants for product formation through enzyme-substrate complex decomposition and for inactivation of catalase are estimated. The organic solvents are characterized by several physical properties: dielectric constant (D), hydrophobicity (log P), concentration of hydroxyl groups ([OH]), polarizability (α), Kamlet-Taft parameter (β) and Kosower parameter (Z). The relationships between the initial rate, kinetic constants and medium properties are analyzed by linear and multiple linear regression.

Quantitative structure-property relationships for predicting sorption of pharmaceuticals to sewage sludge during waste water treatment processes.

PubMed

Berthod, L; Whitley, D C; Roberts, G; Sharpe, A; Greenwood, R; Mills, G A

2017-02-01

Understanding the sorption of pharmaceuticals to sewage sludge during waste water treatment processes is important for understanding their environmental fate and in risk assessments. The degree of sorption is defined by the sludge/water partition coefficient (K d ). Experimental K d values (n=297) for active pharmaceutical ingredients (n=148) in primary and activated sludge were collected from literature. The compounds were classified by their charge at pH7.4 (44 uncharged, 60 positively and 28 negatively charged, and 16 zwitterions). Univariate models relating log K d to log K ow for each charge class showed weak correlations (maximum R 2 =0.51 for positively charged) with no overall correlation for the combined dataset (R 2 =0.04). Weaker correlations were found when relating log K d to log D ow . Three sets of molecular descriptors (Molecular Operating Environment, VolSurf and ParaSurf) encoding a range of physico-chemical properties were used to derive multivariate models using stepwise regression, partial least squares and Bayesian artificial neural networks (ANN). The best predictive performance was obtained with ANN, with R 2 =0.62-0.69 for these descriptors using the complete dataset. Use of more complex Vsurf and ParaSurf descriptors showed little improvement over Molecular Operating Environment descriptors. The most influential descriptors in the ANN models, identified by automatic relevance determination, highlighted the importance of hydrophobicity, charge and molecular shape effects in these sorbate-sorbent interactions. The heterogeneous nature of the different sewage sludges used to measure K d limited the predictability of sorption from physico-chemical properties of the pharmaceuticals alone. Standardization of test materials for the measurement of K d would improve comparability of data from different studies, in the long-term leading to better quality environmental risk assessments. Copyright © 2016 British Geological Survey, NERC. Published by Elsevier B.V. All rights reserved.

Adamantyl- and other polycyclic cage-based conjugates of desferrioxamine B (DFOB) for treating iron-mediated toxicity in cell models of Parkinson's disease.

PubMed

Telfer, Thomas J; Liddell, Jeffrey R; Duncan, Clare; White, Anthony R; Codd, Rachel

2017-04-15

The death of dopaminergic neurons is a major pathological hallmark of Parkinson's disease (PD). Elevated iron within the substantia nigra of the PD brain is thought to catalyze this neuronal death through hydroxyl radical-derived oxidative damage. Removing this excess iron presents a potential therapeutic strategy for PD. Seventeen derivatives of the non-toxic iron chelator desferrioxamine B (DFOB) were prepared by the conjugation of adamantyl- (1-4, 8-12), deconstructed adamantyl units (5-7), norborna(e)ne- (13-16) or bicyclo[2.2.2]octane-based (17) ancillary fragments to the terminal amine group. The range of experimental logP values of 1-17 (logP=0.15-2.82) was greater than water soluble DFOB (logP -2.29), with the increased hydrophobicity designed to improve cell membrane carriage to facilitate intracellular iron sequestration. The first activity screen showed compounds with methyl-substituted adamantyl (1-3), noradamantyl (5), or 1-pentylbicyclo[2.2.2]octane (17) ancillary groups significantly rescued iron-mediated oxidative stress in confluent PD-relevant SK-N-BE2-M17 neuroblastoma cells (M17 cells) exposed to 1,1'-dimethyl-4,4'-bipyridinium (paraquat, PQ) or H 2 O 2 . The second dose-dependence screen ranked 1-3 and 17 as the top candidates (EC 50 ∼10µM) in the rescue of PQ-treated M17 cells. The ancillary fragments of 1-3 and 17 clustered in a region defined by a close-to-zero dipole moment, logP values of 2-2.8 and a surface area:volume ratio of 0.60-0.61. Results of iron leaching studies indicate that the compounds may be operating via mechanisms beyond solely removing intracellular iron. The DFOB conjugates with methyl-substituted adamantyl ancillary groups (1-3) were the top and most consistent performers in this class of compound designed for PD. Copyright © 2017 Elsevier Ltd. All rights reserved.

Bioconcentration, bioaccumulation, and metabolism of pesticides in aquatic organisms.

PubMed

Katagi, Toshiyuki

2010-01-01

The ecotoxicological assessment of pesticide effects in the aquatic environment should normally be based on a deep knowledge of not only the concentration of pesticides and metabolites found but also on the influence of key abiotic and biotic processes that effect rates of dissipation. Although the bioconcentration and bioaccumulation potentials of pesticides in aquatic organisms are conveniently estimated from their hydrophobicity (represented by log K(ow), it is still indispensable to factor in the effects of key abiotic and biotic processes on such pesticides to gain a more precise understanding of how they may have in the natural environment. Relying only on pesticide hydrophobicity may produce an erroneous environmental impact assessment. Several factors affect rates of pesticide dissipation and accumulation in the aquatic environment. Such factors include the amount and type of sediment present in the water and type of diet available to water-dwelling organisms. The particular physiological behavior profiles of aquatic organisms in water, such as capacity for uptake, metabolism, and elimination, are also compelling factors, as is the chemistry of the water. When evaluating pesticide uptake and bioconcentration processes, it is important to know the amount and nature of bottom sediments present and the propensity that the stuffed aquatic organisms have to absorb and process xenobiotics. Extremely hydrophobic pesticides such as the organochlorines and pyrethroids are susceptible to adsorb strongly to dissolved organic matter associated with bottom sediment. Such absorption reduces the bioavailable fraction of pesticide dissolved in the water column and reduces the probable ecotoxicological impact on aquatic organisms living the water. In contrast, sediment dweller may suffer from higher levels of direct exposure to a pesticide, unless it is rapidly degraded in sediment. Metabolism is important to bioconcentration and bioaccumulation processes, as is detoxification and bioactivation. Hydrophobic pesticides that are expected to be highly stored in tissues would not be bioconcentrated if susceptible to biotic transformation by aquatic organisms to more rapidly metabolized to hydrophilic entities are generally less toxic. By analogy, pesticides that are metabolized to similar entities by aquatic species surely are les ecotoxicologically significant. One feature of fish and other aquatic species that makes them more relevant as targets of environmental studies and of regulation is that they may not only become contaminated by pesticides or other chemicals, but that they constitute and important part of the human diet. In this chapter, we provide an overview of the enzymes that are capable of metabolizing or otherwise assisting in the removal of xenobiotics from aquatic species. Many studies have been performed on the enzymes that are responsible for metabolizing xenobiotics. In addition to the use of conventional biochemical methods, such studies on enzymes are increasingly being conducted using immunochemical methods and amino acid or gene sequences analysis. Such studies have been performed in algae, in some aquatic macrophytes, and in bivalva, but less information is available for other aquatic species such as crustacea, annelids, aquatic insecta, and other species. Although their catabolizing activity is often lower than in mammals, oxidases, especially cytochrome P450 enzymes, play a central role in transforming pesticides in aquatic organisms. Primary metabolites, formed from such initial enzymatic action, are further conjugated with natural components such as carbohydrates, and this aids removal form the organisms. The pesticides that are susceptible to abiotic hydrolysis are generally also biotically degraded by various esterases to from hydrophilic conjugates. Reductive transformation is the main metabolic pathway for organochlorine pesticides, but less information on reductive enzymology processes is available. The information on aquatic species, other than fish, that pertains to bioconcentration factors, metabolism, and elimination is rather limited in the literature. The kinds of basic information that is unavailable but is needed on important aquatic species includes biochemistry, physiology, position in food web, habitat, life cycle, etc. such information is very important to obtaining improved ecotoxicology risk assessments for many pesticides and other chemicals. More research attention on the behavior of pesticides in, and affect on many standard aquatic test species (e.g., daphnids, chironomids, oligochaetes and some bivalves) would particularly be welcome. In addition to improving ecotoxicology risk assessments on target species, such information would also assist in better delineating affects on species at higher trophic levels that are predaceous on the target species. There is also need for designing and employing more realistic approaches to measure bioconcentration and bioaccumulation, and ecotoxicology effects of pesticides in natural environment. The currently employed steady-state laboratory exposure studies are insufficient to deal with the complexity of parameters that control the contrasts to the abiotic processes of pesticide investigated under the strictly controlled conditions, each process is significantly affected in the natural environment not only by the site-specific chemistry of water and sediment but also by climate. From this viewpoint, ecotoxicological assessment should be conducted, together with the detailed analyses of abiotic processes, when higher-tier mesocosm studies are performed. Moreover, in-depth investigation is needed to better understand the relationship between pesticide residues in organisms and associated ecotoxicological endpoints. The usual exposure assessment is based on apparent (nominal) concentrations fo pesticides, and the residues of pesticides or their metabolites in the organisms are not considered in to the context of ecotoxicological endpoints. Therefore, more metabolic and tissue distribution information for terminal pesticide residues is needed for aquatic species both in laboratory settings and in higher-tier (microcosm, mesocosm) studies.

Application of Snyder-Dolan Classification Scheme to the Selection of “Orthogonal” Columns for Fast Screening for Illicit Drugs and Impurity Profiling of Pharmaceuticals - I. Isocratic Elution

PubMed Central

Fan, Wenzhe; Zhang, Yu; Carr, Peter W.; Rutan, Sarah C.; Dumarey, Melanie; Schellinger, Adam P.; Pritts, Wayne

2011-01-01

Fourteen judiciously selected reversed-phase columns were tested with 18 cationic drug solutes under the isocratic elution conditions advised in the Snyder-Dolan (S-D) hydrophobic subtraction method of column classification. The standard errors (S.E.) of the least squares regressions of log k′ vs. log k′REF were obtained for a given column against a reference column and used to compare and classify columns based on their selectivity. The results are consistent with those obtained with a study of the 16 test solutes recommended by Snyder and Dolan. To the extent that these drugs are representative these results show that the S-D classification scheme is also generally applicable to pharmaceuticals under isocratic conditions. That is, those columns judged to be similar based on the S-D 16 solutes were similar based on the 18 drugs; furthermore those columns judged to have significantly different selectivities based on the 16 S-D probes appeared to be quite different for the drugs as well. Given that the S-D method has been used to classify more than 400 different types of reversed phases the extension to cationic drugs is a significant finding. PMID:19698948

Application of an oregano oil nanoemulsion to the control of foodborne bacteria on fresh lettuce.

PubMed

Bhargava, Kanika; Conti, Denise S; da Rocha, Sandro R P; Zhang, Yifan

2015-05-01

Although antimicrobial activities of plant essential oils are well documented, challenges remain as to their application in fresh produce due to the hydrophobic nature of essential oils. Oregano oil nanoemulsions were formulated with a food-grade emulsifier and evaluated for their efficacy in inactivating the growth of foodborne bacteria on fresh lettuce. Lettuce was artificially inoculated with Listeria monocytogenes, Salmonella Typhimurium and Escherichia coli O157:H7, followed by a one-minute dipping in oregano oil nanoemulsions (0.05% or 0.1%). Samples were stored at 4 °C and enumerated for bacteria at fixed intervals (0 h, 3 h, 24 h, and 72 h). Compared to control, 0.05% nanoemulsion showed an up to 3.44, 2.31, and 3.05 log CFU/g reductions in L. monocytogenes, S. Typhimurium, and E. coli O157:H7, respectively. Up to 3.57, 3.26, and 3.35 log CFU/g reductions were observed on the same bacteria by the 0.1% treatment. Scanning Electron Microscopy (SEM) demonstrated disrupted bacterial membranes due to the oregano oil treatment. The data suggest that applying oregano oil nanoemulsions to fresh produce may be an effective antimicrobial control strategy. Copyright © 2014 Elsevier Ltd. All rights reserved.

SEM Analysis of Surface Impact on Biofilm Antibiotic Treatment.

PubMed

Gomes, Luciana Calheiros; Mergulhão, Filipe José

2017-01-01

The aim of this work was to use scanning electron microscopy (SEM) to investigate the effect of ampicillin treatment on Escherichia coli biofilms formed on two surface materials with different properties, silicone (SIL) and glass (GLA). Epifluorescence microscopy (EM) was initially used to assess biofilm formation and killing efficiency on both surfaces. This technique showed that higher bacterial colonization was obtained in the hydrophobic SIL than in the hydrophilic GLA. It has also shown that higher biofilm inactivation was attained for GLA after the antibiotic treatment (7-log reduction versus 1-log reduction for SIL). Due to its high resolution and magnification, SEM enabled a more detailed analysis of the antibiotic effect on biofilm cells, complementing the killing efficiency information obtained by EM. SEM micrographs revealed that ampicillin-treated cells have an elongated form when compared to untreated cells. Additionally, it has shown that different materials induced different levels of elongation on cells exposed to antibiotic. Biofilms formed on GLA showed a 37% higher elongation than those formed on SIL. Importantly, cell elongation was related to viability since ampicillin had a higher bactericidal effect on GLA-formed biofilms. These findings raise the possibility of using SEM for understanding the efficacy of antimicrobial treatments by observation of biofilm morphology.

QSAR, QSPR and QSRR in Terms of 3-D-MoRSE Descriptors for In Silico Screening of Clofibric Acid Analogues.

PubMed

Di Tullio, Maurizio; Maccallini, Cristina; Ammazzalorso, Alessandra; Giampietro, Letizia; Amoroso, Rosa; De Filippis, Barbara; Fantacuzzi, Marialuigia; Wiczling, Paweł; Kaliszan, Roman

2012-07-01

A series of 27 analogues of clofibric acid, mostly heteroarylalkanoic derivatives, have been analyzed by a novel high-throughput reversed-phase HPLC method employing combined gradient of eluent's pH and organic modifier content. The such determined hydrophobicity (lipophilicity) parameters, log kw , and acidity constants, pKa , were subjected to multiple regression analysis to get a QSRR (Quantitative StructureRetention Relationships) and a QSPR (Quantitative Structure-Property Relationships) equation, respectively, describing these pharmacokinetics-determining physicochemical parameters in terms of the calculation chemistry derived structural descriptors. The previously determined in vitro log EC50 values - transactivation activity towards PPARα (human Peroxisome Proliferator-Activated Receptor α) - have also been described in a QSAR (Quantitative StructureActivity Relationships) equation in terms of the 3-D-MoRSE descriptors (3D-Molecule Representation of Structures based on Electron diffraction descriptors). The QSAR model derived can serve for an a priori prediction of bioactivity in vitro of any designed analogue, whereas the QSRR and the QSPR models can be used to evaluate lipophilicity and acidity, respectively, of the compounds, and hence to rational guide selection of structures of proper pharmacokinetics. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis and physicochemical properties of the furan dicarboxylic acid, 3-carboxy-4-methyl-5-propyl-2-furanpropanoic acid, an inhibitor of plasma protein binding in uraemia.

PubMed

Costigan, M G; Gilchrist, T L; Lindup, W E

1996-06-01

The furan dicarboxylic acid, 3-carboxy-4-methyl-5-propyl-2-furanpropanoic acid (5-propyl FPA) accumulates in the plasma of patients with chronic renal failure and is a major contributor to the drug binding defect of uraemic plasma. This acid has also been implicated in several other aspects of the uraemic syndrome: anaemia, irregularities of thyroid function, neurological symptoms and inhibition of active tubular secretion. The acid is not commercially available and its synthesis, starting with Meldrum's acid and methyl succinyl chloride, is described. The pKa values were measured by titration and values of 3.2 and 3.6 respectively were assigned to the carboxylic acid groups attached directly to the ring at position 3 and at position 2 (on the side-chain). The partition coefficient (log P) between hydrochloric acid and octanol was 1.2 and the distribution coefficient (log D; octanol-phosphate buffer pH 7.4) was -0.59. The pKa values and the degree of hydrophobic character of 5-propyl FPA are consistent with those of other protein-bound acids which undergo active tubular secretion by the kidney and this substance may serve as an endogenous marker for the effects of drugs and disease on this process.

Molecular basis of quantitative structure-properties relationships (QSPR): a quantum similarity approach.

PubMed

Ponec, R; Amat, L; Carbó-Dorca, R

1999-05-01

Since the dawn of quantitative structure-properties relationships (QSPR), empirical parameters related to structural, electronic and hydrophobic molecular properties have been used as molecular descriptors to determine such relationships. Among all these parameters, Hammett sigma constants and the logarithm of the octanol-water partition coefficient, log P, have been massively employed in QSPR studies. In the present paper, a new molecular descriptor, based on quantum similarity measures (QSM), is proposed as a general substitute of these empirical parameters. This work continues previous analyses related to the use of QSM to QSPR, introducing molecular quantum self-similarity measures (MQS-SM) as a single working parameter in some cases. The use of MQS-SM as a molecular descriptor is first confirmed from the correlation with the aforementioned empirical parameters. The Hammett equation has been examined using MQS-SM for a series of substituted carboxylic acids. Then, for a series of aliphatic alcohols and acetic acid esters, log P values have been correlated with the self-similarity measure between density functions in water and octanol of a given molecule. And finally, some examples and applications of MQS-SM to determine QSAR are presented. In all studied cases MQS-SM appeared to be excellent molecular descriptors usable in general QSPR applications of chemical interest.

Molecular basis of quantitative structure-properties relationships (QSPR): A quantum similarity approach

NASA Astrophysics Data System (ADS)

Ponec, Robert; Amat, Lluís; Carbó-dorca, Ramon

1999-05-01

Since the dawn of quantitative structure-properties relationships (QSPR), empirical parameters related to structural, electronic and hydrophobic molecular properties have been used as molecular descriptors to determine such relationships. Among all these parameters, Hammett σ constants and the logarithm of the octanol- water partition coefficient, log P, have been massively employed in QSPR studies. In the present paper, a new molecular descriptor, based on quantum similarity measures (QSM), is proposed as a general substitute of these empirical parameters. This work continues previous analyses related to the use of QSM to QSPR, introducing molecular quantum self-similarity measures (MQS-SM) as a single working parameter in some cases. The use of MQS-SM as a molecular descriptor is first confirmed from the correlation with the aforementioned empirical parameters. The Hammett equation has been examined using MQS-SM for a series of substituted carboxylic acids. Then, for a series of aliphatic alcohols and acetic acid esters, log P values have been correlated with the self-similarity measure between density functions in water and octanol of a given molecule. And finally, some examples and applications of MQS-SM to determine QSAR are presented. In all studied cases MQS-SM appeared to be excellent molecular descriptors usable in general QSPR applications of chemical interest.

Analyzing chromatographic data using multilevel modeling.

PubMed

Wiczling, Paweł

2018-06-01

It is relatively easy to collect chromatographic measurements for a large number of analytes, especially with gradient chromatographic methods coupled with mass spectrometry detection. Such data often have a hierarchical or clustered structure. For example, analytes with similar hydrophobicity and dissociation constant tend to be more alike in their retention than a randomly chosen set of analytes. Multilevel models recognize the existence of such data structures by assigning a model for each parameter, with its parameters also estimated from data. In this work, a multilevel model is proposed to describe retention time data obtained from a series of wide linear organic modifier gradients of different gradient duration and different mobile phase pH for a large set of acids and bases. The multilevel model consists of (1) the same deterministic equation describing the relationship between retention time and analyte-specific and instrument-specific parameters, (2) covariance relationships relating various physicochemical properties of the analyte to chromatographically specific parameters through quantitative structure-retention relationship based equations, and (3) stochastic components of intra-analyte and interanalyte variability. The model was implemented in Stan, which provides full Bayesian inference for continuous-variable models through Markov chain Monte Carlo methods. Graphical abstract Relationships between log k and MeOH content for acidic, basic, and neutral compounds with different log P. CI credible interval, PSA polar surface area.

Inosine and 2'-deoxyinosine and their synthetic analogues: lipophilicity in the relation to their retention in reversed-phase liquid chromatography and the stability characteristics.

PubMed

Novotny, L; Abdel-Hamid, M; Hamza, H

2000-12-01

The purines and among them inosine synthetic nucleoside derivatives and analogues belong to a group of compounds to which the attention is being paid because of their biological activities. Relationships of their various parameters are being investigated because of their effect on biological (antineoplastic, virostatic, immunosuppressive) properties. Hydrophobicity parameters expressed as the logarithm of the partition coefficient (log P) and the capacity factor k' for naturally occurring inosine, 2'-deoxyinosine, 2'-deoxyadenosine and 2'-deoxyguanosine and for inosine synthetic analogues 5'-deoxyinosine, 5'-chloro-5'-deoxyinosine and 2',3'-dideoxyinosine were measured. The effect of methanol percentage in the mobile phase and its pH on the retention of the studied compounds in a reversed-phase system was also examined. There was a good correlation between the lipophilicity expressed as log P and capacity factor k'. It was also determined that dissociation has a marginal effect on capacity factor k' in this group of nucleoside derivatives as the k' values were almost unchanged at various pH of the mobile phase used. The stability of the all investigated compounds was investigated in basic, neutral and acidic conditions. The values of the reaction constant k1 were calculated and effects of nucleoside structural characteristic on stability are discussed.

Environmental risk assessment of selected organic chemicals based on TOC test and QSAR estimation models.

PubMed

Chi, Yulang; Zhang, Huanteng; Huang, Qiansheng; Lin, Yi; Ye, Guozhu; Zhu, Huimin; Dong, Sijun

2018-02-01

Environmental risks of organic chemicals have been greatly determined by their persistence, bioaccumulation, and toxicity (PBT) and physicochemical properties. Major regulations in different countries and regions identify chemicals according to their bioconcentration factor (BCF) and octanol-water partition coefficient (Kow), which frequently displays a substantial correlation with the sediment sorption coefficient (Koc). Half-life or degradability is crucial for the persistence evaluation of chemicals. Quantitative structure activity relationship (QSAR) estimation models are indispensable for predicting environmental fate and health effects in the absence of field- or laboratory-based data. In this study, 39 chemicals of high concern were chosen for half-life testing based on total organic carbon (TOC) degradation, and two widely accepted and highly used QSAR estimation models (i.e., EPI Suite and PBT Profiler) were adopted for environmental risk evaluation. The experimental results and estimated data, as well as the two model-based results were compared, based on the water solubility, Kow, Koc, BCF and half-life. Environmental risk assessment of the selected compounds was achieved by combining experimental data and estimation models. It was concluded that both EPI Suite and PBT Profiler were fairly accurate in measuring the physicochemical properties and degradation half-lives for water, soil, and sediment. However, the half-lives between the experimental and the estimated results were still not absolutely consistent. This suggests deficiencies of the prediction models in some ways, and the necessity to combine the experimental data and predicted results for the evaluation of environmental fate and risks of pollutants. Copyright © 2016. Published by Elsevier B.V.

Effect of clarification process on the removal of pesticide residues in red wine and comparison with white wine.

PubMed

Doulia, Danae S; Anagnos, Efstathios K; Liapis, Konstantinos S; Klimentzos, Demetrios A

2018-04-30

The aim of this study was to determine the potential of seven clarifying agents to remove pesticides in red wine. The presence of pesticides in wine consists a great problem for winemakers and therefore, results on pesticide removal by clarification are very useful for taking a decision on the appropriate adsorbent. The selection of an efficient adsorbent can be based on data correlating pesticide removal in red wine to pesticides' properties, given the great number and variety of pesticides used. So, this experimental work is focused on the collection of results with regard to pesticide removal by clarification using a great number of pesticides and fining agents. A Greek red wine, fortified with single solutions and mixtures of 23 or 9 pesticides was studied. The seven fining agents, used at two concentrations, were activated carbon, bentonite, polyvinylpolypyrrolidone (PVPP), gelatin, egg albumin, isinglass-fish glue, and casein. Pesticides were selected with a wide range of properties (octanol-water partition coefficient (log K ow ) 2.7-6.3 and water solubility 0.0002-142) and belong to 11 chemical groups. Solid phase extraction (SPE) followed by gas chromatography (GC) with electron capture detector (ECD) were performed to analyze pesticide residues of the clarified fortified wine. The correlation of the clarifying agents' effectiveness to pesticide's chemical structure and properties (log K ow , water solubility) was investigated. The antagonistic and/or synergistic effects, occurring among the pesticides in the mixtures, were calculated by indices. Pesticide removal effectiveness results of the red wine were compared to those obtained from a white wine under the same experimental conditions and discussed. The order of decreasing adsorbent effectiveness (mixture of 23 pesticides) was: activated carbon 40% > gelatin 23% > egg albumin 21% > PVPP 18% > casein 12% > bentonite 7%. Isinglass showed 12% removal at the highest permitted concentration. In the case of 9 pesticides mixture, the effectiveness was quite higher but the order remained the same compared to 23 pesticides mixture. The removal of each pesticide from its single solution was generally the highest (particularly for hydrophobic pesticides). Adsorption on fining agents is increased by increasing hydrophobicity and decreasing hydrophilicity of organic pesticide molecules.

Routes of uptake of diclofenac, fluoxetine, and triclosan into sediment-dwelling worms.

PubMed

Karlsson, Maja V; Marshall, Stuart; Gouin, Todd; Boxall, Alistair B A

2016-04-01

The present study investigated the route and degree of uptake of 2 ionizable pharmaceuticals (diclofenac and fluoxetine) and 1 ionizable compound used in personal care products (triclosan) into the sediment-dwelling worm Lumbriculus variegatus. Studies were done on complete worms ("feeding") and worms where the head was absent ("nonfeeding") using (14) C-labeled ingredients. Biota sediment accumulation factors (BSAF), based on uptake of (14) C, for feeding worms increased in the order fluoxetine (0.3) < diclofenac (0.5) < triclosan (9), which is correlated with a corresponding increase in log octanol-water partition coefficient. Biota sediment accumulation factor estimates are representative of maximum values because the degree of biotransformation in the worms was not quantified. Although no significant differences were seen between the uptake of diclofenac and that of fluoxetine in feeding and nonfeeding worms, uptake of the more hydrophobic antimicrobial, triclosan, into the feeding worms was significantly greater than that in the nonfeeding worms, with the 48-h BSAF for feeding worms being 36% higher than that for the nonfeeding worms. The results imply that dietary uptake contributes to the uptake of triclosan, which may be a result of the high hydrophobicity of the compound. Models that estimate exposure of ionizable substances may need to consider uptake from both the water column and food, particularly when assessing risks from dynamic exposures to organic contaminants. © 2015 SETAC.

Bioconcentration of chlorinated aromatic hydrocarbons in aquatic macrophytes

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

Gobas, F.A.P.C.; McNeil, E.J.; Lovett-Doust, L.

1991-05-01

This study reports the bioconcentration and the uptake and elimination kinetics of a series of nonreactive, hydrophobic organic substances in the submerged aquatic macrophyte Myriophyllum spicatum. The tested substances represent a wide range of aqueous solubilities and 1-octanol-water partition coefficients (K{sub OW}). The plant-water bioconcentration factor is shown to follow a linear relationship with the octanol-water partition coefficient for all chemicals, including the superhydrophobic chemicals with log K{sub OW} up to 8.3. The uptake and elimination rate constants tend to follow a biphasic relationship with K{sub OW}. A kinetic model is developed for organic chemical bioconcentration is submerged aquatic macrophytemore » species. This model is applied to the Detroit River and Lake St. Clair to illustrate the role of aquatic macrophytes in chemical dynamics in aquatic systems.« less

New insight into pesticide partition coefficient Kd for modelling pesticide fluvial transport: application to an agricultural catchment in south-western France.

PubMed

Boithias, Laurie; Sauvage, Sabine; Merlina, Georges; Jean, Séverine; Probst, Jean-Luc; Sánchez Pérez, José Miguel

2014-03-01

Pesticides applied on crops are leached with rainfall to groundwater and surface water. They threat the aquatic environment and may render water unfit for human consumption. Pesticide partitioning is one of the pesticide fate processes in the environment that should be properly formalised in pesticide fate models. Based on the analysis of 7 pesticide molecules (alachlor, atrazine, atrazine's transformation product deethylatrazine or DEA, isoproturon, tebuconazole and trifluralin) sampled from July 2009 to October 2010 at the outlet of the river Save (south-western France), the objectives of this study were (1) to check which of the environmental factors (discharge, pH, concentrations of total suspended matter (TSM), dissolved organic carbon (DOC) and particulate organic carbon (POC) could control the pesticide sorption dynamic, and (2) to establish a relationship between environmental factors, the partition coefficient Kd and the octanol/water distribution coefficient Kow. The comparison of physico-chemical parameters values during low flow and high flow shows that discharge, TSM and POC are the factors most likely controlling the pesticide sorption processes in the Save river network, especially for lower values of TSM (below 13mgL(-1)). We therefore express Kd depending on the widely literature-related variable Kow and on the commonly simulated variable TSM concentration. The equation can be implemented in any model describing the fluvial transport and fate of pesticides in both dissolved and sorbed phases, thus, Kd becomes a variable in time and space. The Kd calculation method can be applied to a wide range of catchments and organic contaminants. Copyright © 2013 Elsevier Ltd. All rights reserved.

Measurement of Setschenow constants for six hydrophobic compounds in simulated brines and use in predictive modeling for oil and gas systems.

PubMed

Burant, Aniela; Lowry, Gregory V; Karamalidis, Athanasios K

2016-02-01

Treatment and reuse of brines, produced from energy extraction activities, requires aqueous solubility data for organic compounds in saline solutions. The presence of salts decreases the aqueous solubility of organic compounds (i.e. salting-out effect) and can be modeled using the Setschenow Equation, the validity of which has not been assessed in high salt concentrations. In this study, we used solid-phase microextraction to determine Setschenow constants for selected organic compounds in aqueous solutions up to 2-5 M NaCl, 1.5-2 M CaCl2, and in Na-Ca binary electrolyte solutions to assess additivity of the constants. These compounds exhibited log-linear behavior up to these high NaCl concentrations. Log-linear decreases in solubility with increasing salt concentration were observed up to 1.5-2 M CaCl2 for all compounds, and added to a sparse database of CaCl2 Setschenow constants. Setschenow constants were additive in binary electrolyte mixtures. New models to predict CaCl2 and KCl Setschenow constants from NaCl Setschenow constants were developed, which successfully predicted the solubility of the compounds measured in this study. Overall, data show that the Setschenow Equation is valid for a wide range of salinity conditions typically found in energy-related technologies. Copyright © 2015 Elsevier Ltd. All rights reserved.

Dispersive micro-solid-phase extraction of benzoylurea insecticides in honey samples with a β-cyclodextrin-modified attapulgite composite as sorbent.

PubMed

Zhang, Panjie; Cui, Xiangqian; Yang, Xiaoling; Zhang, Sanbing; Zhou, Wenfeng; Gao, Haixiang; Lu, Runhua

2016-01-01

A β-cyclodextrin-modified attapulgite composite was prepared and used as a dispersive micro-solid-phase extraction sorbent for the determination of benzoylurea insecticides in honey samples. Parameters that may influence the extraction efficiency, such as the type and volume of the eluent, the amount of the sorbent, the extraction time and the ionic strength were investigated and optimized using batch and column procedures. Under optimized conditions, good linearity was obtained for all of the tested compounds, with R(2) values of at least 0.9834. The limits of detection were determined in the range of 0.2-1.0 μg/L. The recoveries of the four benzoylurea insecticides in vitex honey and acacia honey increased from 15.2 to 81.4% and from 14.2 to 82.0%, respectively. Although the β-cyclodextrin-modified attapulgite composite did not show a brilliant adsorption capacity for the selected benzoylurea insecticides, it exhibited a higher adsorption capacity toward relatively hydrophobic compounds, such as chlorfluazuron and hexaflumuron (recoveries in vitex honey samples ranged from 70.0 to 81.4% with a precision of 1.0-3.7%). It seemed that the logPow of the benzoylurea insecticides is related to their recoveries. The results confirmed the possibility of using cyclodextrin-modified palygorskite in the determination of relatively hydrophobic trace pharmaceutical residues. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A flow-through aqueous standard generation system for thin film microextraction investigations of UV filters and biocides partitioning to different environmental compartments.

PubMed

Ahmadi, Fardin; Sparham, Chris; Pawliszyn, Janusz

2017-11-01

In this paper problems associated with preparation of aqueous standard of highly hydrophobic compounds such as partial precipitation, being lost on the surfaces, low solubility in water and limited sample volume for accurate determination of their distribution coefficients are addressed. The following work presents two approaches that utilize blade thin film microextraction (TFME) to investigate partitioning of UV filters and biocides to humic acid (dissolved organic carbon) and sediment. A steady-state concentration of target analytes in water was generated using a flow-through aqueous standard generation (ASG) system. Dialysis membranes, a polytetrafluoroethylene permeation tube, and a frit porous (0.5 μm) coated by epoxy glue were basic elements used for preparation of the ASG system. In the currently presented study, negligible depletion TFME using hydrophilic-lipophilic balance (HLB) and octadecyl silica-based (C18) sorbents was employed towards the attainment of free concentration values of target analytes in the studied matrices. Thin film geometry provided a large volume of extraction phase, which improved the sensitivity of the method towards highly matrix-bound analytes. Extractions were performed in the equilibrium regime so as to prevent matrix effects and with aims to reach maximum method sensitivity for all analytes under study. Partitioning of analytes on dissolved organic carbon (DOC) was investigated in ASG to facilitate large sample volume conditions. Binding percentages and DOC distribution coefficients (Log K DOC ) ranged from 20 to 98% and 3.71-6.72, respectively. Furthermore, sediment-water partition coefficients (K d ), organic-carbon normalized partition coefficients (Log K OC ), and DOC distribution coefficients (Log K DOC ) were investigated in slurry sediment, and ranged from 33 to 2860, 3.31-5.24 and 4.52-5.75 Lkg -1 , respectively. The obtained results demonstrated that investigations utilizing ASG and TFME can yield reliable binding information for compounds with high log K OW values. This information is useful for study of fate, transport, and ecotoxicological effects of UV filters and biocides in aquatic environment. Copyright © 2017 Elsevier Ltd. All rights reserved.

QSAR studies in substituted 1,2,3,4,6,7,12,12a-octa-hydropyrazino[2',1':6,1]pyrido[3,4-b]indoles--a potent class of neuroleptics.

PubMed

Saxena, Anil K; Ram, Siya; Saxena, Mridula; Singh, Nidhi; Prathipati, Philip; Jain, Padam C; Singh, H K; Anand, Nitya

2003-05-01

A series of nineteen substituted 1,2,3,4,6,7,12,12a-octahydropyrazino[2',1':6,1]pyrido[3, 4-b]indoles analogues of neuroleptic drug, Centbutindole have been studied using quantitative structure-activity relationship analysis. The derived models display good fits to the experimental data (r>or=0.75) having good predictive power (r(cv)>or=0.688). The best model describes a high correlation between predicted and experimental activity data (r=0.967). Statistical analysis of the equation populations indicates that hydrophobicity (as measured by pi(R), logP(o/w) and SlogP_VSA8), dipole y and structural parameters in terms of indicator variable, (In(1)) and globularity are important variables in describing the variation in the neuroleptic activity in the series.

QuEChERS sample preparation for the determination of pesticides and other organic residues in environmental matrices: a critical review.

PubMed

Bruzzoniti, Maria Concetta; Checchini, Leonardo; De Carlo, Rosa Maria; Orlandini, Serena; Rivoira, Luca; Del Bubba, Massimo

2014-07-01

Quick, Easy, Cheap, Effective, Rugged, and Safe (QuEChERS) is an extraction and clean-up technique originally developed for recovering pesticide residues from fruits and vegetables. Since its introduction, and until December 2013, about 700 papers have been published using the QuEChERS technique, according to a literature overview carried out using SciFinder, Elsevier SciVerse, and Google search engines. Most of these papers were dedicated to pesticide multiresidue analysis in food matrices, and this topic has been thoroughly reviewed over recent years. The QuEChERS approach is now rapidly developing beyond its original field of application to analytes other than pesticides, and matrices other than food, such as biological fluids and non-edible plants, including Chinese medicinal plants. Recently, the QuEChERS concept has spread to environmental applications by analyzing not only pesticides but also other compounds of environmental concern in soil, sediments, and water. To the best of our knowledge, QuEChERS environmental applications have not been reviewed so far; therefore, in this contribution, after a general discussion on the evolution and changes of the original QuEChERS method, a critical survey of the literature regarding environmental applications of conventional and modified QuEChERS methodology is provided. The overall recoveries obtained with QuEChERS and other extraction approaches (e.g., accelerated solvent extraction, ultrasonic solvent extraction, liquid/solid extraction, and soxhlet extraction) were compared, providing evidence for QuEChERS higher recoveries for various classes of compounds, such as biopesticides, chloroalkanes, phenols, and perfluoroalkyl substances. The role of physicochemical properties of soil (i.e., clay and organic carbon content, as well as cation exchange capacity) and target analytes (i.e., log KOW, water solubility, and vapor pressure) were also evaluated in order to interpret recovery and matrix effect data.

Biodegradability relationships among propylene glycol substances in the Organization for Economic Cooperation and Development ready- and seawater biodegradability tests.

PubMed

West, Robert J; Davis, John W; Pottenger, Lynn H; Banton, Marcy I; Graham, Cynthia

2007-05-01

Eight propylene glycol substances, ranging from 1,2-propanediol to a poly(propylene glycol) (PPG) having number-average molecular weight (M(n)) of 2,700 (i.e., PPG 2700), were evaluated in the Organization for Economic Cooperation and Development (OECD) ready- and seawater biodegradability tests. Uniformity in test parameters, such as inoculum source/density and test substance concentrations, combined with frequent measurements of O2 consumption and CO2 evolution, revealed unexpected biodegradability trends across this family of substances. Biodegradability in both tests decreased with increased number of oxy-propylene repeating units (n = 1, 2, 3, 4) of the oligomeric propylene glycols (PGs). However, this trend was reversed for the PPG polymers, and increased biodegradability was observed with increases of average n to seven, 17, and 34 (M(n) = 425, 1,000, and 2,000, respectively). This relationship between molecular weight and biodegradability was reversed again when average n was incremented from 34 (PPG 2000) to 46 (PPG 2700). Six of the tested substances (n = 1, 2, 3, 7, 17, and 34) met the OECD-specified criteria for "ready biodegradability," whereas the tetrapropylene glycol (n = 4) and PPG 2700 substances failed to meet these criteria. Biodegradation half-lives for these eight substances ranged from 3.8 d (PPG 2000) to 33.2 d (PPG 2700) in the ready test, and from 13.6 (PG) to 410 d (PPG 2700) in seawater. Biodegradation half-lives in seawater were significantly correlated with half-lives determined in the ready test. However, half-lives in both tests were correlated poorly with molecular weight, water solubility, and log K(ow). It is speculated that the molecular conformation of these substances, perhaps more so than these other physicochemical properties, has an important role in influencing biodegradability of the propylene glycol substances.

Absorption and biotransformation of polybrominated diphenyl ethers DE-71 and DE-79 in chicken (Gallus gallus), mallard (Anas platyrhynchos), American kestrel (Falco sparverius) and black-crowned night-heron (Nycticorax nycticorax) eggs

USGS Publications Warehouse

McKernan, Moira A.; Rattner, Barnett A.; Hatfield, Jeff S.; Hale, Robert C.; Ottinger, Mary Ann

2010-01-01

We recently reported that air cell administration of penta-brominated diphenyl ether (penta-BDE; DE-71) evokes biochemical and immunologic effects in chicken (Gallus gallus) embryos at very low doses, and impairs pipping (i.e., stage immediately prior to hatching) and hatching success at 1.8 ug g-1 egg (actual dose absorbed) in American kestrels (Falco sparverius). I n the present study, absorption of polybrominated diphenyl ether (PBDE) congeners was measured following air cell administration of a penta-BDE mixture (11.1 ug DE-71 g-1 egg) or an octa-brominated diphenyl ether mixture (octa-BDE; DE-79; 15.4 ug DE-79 g-1 egg). Uptake of PBDE congeners was measured at 24 h post-injection, midway through incubation, and at pipping in chicken, mallard (Anas platyrhynchos), and American kestrel egg contents, and at the end of incubation in black-crowned night-heron (Nycticorax nycticorax) egg contents. Absorption of penta-BDE and octa-BDE from the air cell into egg contents occurred throughout incubation; at pipping, up to 29.6% of penta-BDE was absorbed, but only 1.40-6.48% of octa-BDE was absorbed. Higher brominated congeners appeared to be absorbed more slowly than lower brominated congeners, and uptake rate was inversely proportional to the log Kow of predominant BDE congeners. Six congeners or co-eluting pairs of congeners were detected in penta-BDE-treated eggs that were not found in the dosing solution suggesting debromination in the developing embryo, extraembryonic membranes, and possibly even in the air cell membrane. This study demonstrates the importance of determining the fraction of xenobiotic absorbed into the egg following air cell administration for estimation of the lowest-observed-effect level.

Coupled Abiotic-Biotic Degradation of Bisphenol A

NASA Astrophysics Data System (ADS)

Im, J.; Prevatte, C.; Campagna, S. R.; Loeffler, F.

2014-12-01

Bisphenol A (BPA) is a ubiquitous environmental contaminant with weak estrogenic activity. BPA is readily biodegradable with oxygen available, but is recalcitrant to microbial degradation under anoxic conditions. However, BPA is susceptible to abiotic transformation under anoxic conditions. To better understand the fate of BPA in anoxic environments, the kinetics of BPA transformation by manganese oxide (d-MnO2) were investigated. BPA was rapidly transformed by MnO2 with a pseudo-first-order rate constant of 0.413 min-1. NMR and LC-MS analyses identified 4-hydroxycumyl alcohol (HCA) as a major intermediate. Up to 64% of the initial amount of BPA was recovered as HCA within 5 min, but the conversion efficiency decreased with time, suggesting that HCA was further degraded by MnO2. Further experiments confirmed that HCA was also susceptible to transformation by MnO2, albeit at 5-fold lower rates than BPA transformation. Mass balance approaches suggested that HCA was the major BPA transformation intermediate, but other compounds may also be formed. The abiotic transformation of BPA by MnO2 was affected by pH, and 10-fold higher transformation rates were observed at pH 4.5 than at pH 10. Compared to BPA, HCA has a lower octanol-water partitioning coefficient (Log Kow) of 0.76 vs 2.76 for BPA and a higher aqueous solubility of 2.65 g L-1 vs 0.31 g L-1 for BPA, suggesting higher mobility of HCA in the environment. Microcosms established with freshwater sediment materials collected from four geographically distinct locations and amended with HCA demonstrated rapid HCA biodegradation under oxic, but not under anoxic conditions. These findings suggest that BPA is not inert under anoxic conditions and abiotic reactions with MnO2 generate HCA, which has increased mobility and is susceptible to aerobic degradation. Therefore, coupled abiotic-biotic processes can affect the fate and longevity of BPA in terrestrial environments.

Removal of MS2, Qβ and GA bacteriophages during drinking water treatment at pilot scale.

PubMed

Boudaud, Nicolas; Machinal, Claire; David, Fabienne; Fréval-Le Bourdonnec, Armelle; Jossent, Jérôme; Bakanga, Fanny; Arnal, Charlotte; Jaffrezic, Marie Pierre; Oberti, Sandrine; Gantzer, Christophe

2012-05-15

The removal of MS2, Qβ and GA, F-specific RNA bacteriophages, potential surrogates for pathogenic waterborne viruses, was investigated during a conventional drinking water treatment at pilot scale by using river water, artificially and independently spiked with these bacteriophages. The objective of this work is to develop a standard system for assessing the effectiveness of drinking water plants with respect to the removal of MS2, Qβ and GA bacteriophages by a conventional pre-treatment process (coagulation-flocculation-settling-sand filtration) followed or not by an ultrafiltration (UF) membrane (complete treatment process). The specific performances of three UF membranes alone were assessed by using (i) pre-treated water and (ii) 0.1 mM sterile phosphate buffer solution (PBS), spiked with bacteriophages. These UF membranes tested in this work were designed for drinking water treatment market and were also selected for research purpose. The hypothesis serving as base for this study was that the interfacial properties for these three bacteriophages, in terms of electrostatic charge and the degree of hydrophobicity, could induce variations in the removal performances achieved by drinking water treatments. The comparison of the results showed a similar behaviour for both MS2 and Qβ surrogates whereas it was particularly atypical for the GA surrogate. The infectious character of MS2 and Qβ bacteriophages was mostly removed after clarification followed by sand filtration processes (more than a 4.8-log reduction) while genomic copies were removed at more than a 4.0-log after the complete treatment process. On the contrary, GA bacteriophage was only slightly removed by clarification followed by sand filtration, with less than 1.7-log and 1.2-log reduction, respectively. After the complete treatment process achieved, GA bacteriophage was removed with less than 2.2-log and 1.6-log reduction, respectively. The effectiveness of the three UF membranes tested in terms of bacteriophages removal showed significant differences, especially for GA bacteriophage. These results could provide recommendations for drinking water suppliers in terms of selection criteria for membranes. MS2 bacteriophage is widely used as a surrogate for pathogenic waterborne viruses in Europe and the United States. In this study, the choice of MS2 bacteriophage as the best surrogate to be used for assessment of the effectiveness of drinking water treatment in removal of pathogenic waterborne viruses in worst conditions is clearly challenged. It was shown that GA bacteriophage is potentially a better surrogate as a worst case than MS2. Considering GA bacteriophage as the best surrogate in this study, a chlorine disinfection step could guaranteed a complete removal of this model and ensure the safety character of drinking water plants. Copyright © 2012 Elsevier Ltd. All rights reserved.

A Recombinant Respiratory Syncytial Virus Vaccine Candidate Attenuated by a Low-Fusion F Protein Is Immunogenic and Protective against Challenge in Cotton Rats

PubMed Central

Rostad, Christina A.; Stobart, Christopher C.; Gilbert, Brian E.; Pickles, Ray J.; Hotard, Anne L.; Meng, Jia; Blanco, Jorge C. G.; Moin, Syed M.; Graham, Barney S.; Piedra, Pedro A.

2016-01-01

ABSTRACT Although respiratory syncytial virus (RSV) is the leading cause of lower respiratory tract infections in infants, a safe and effective vaccine is not yet available. Live-attenuated vaccines (LAVs) are the most advanced vaccine candidates in RSV-naive infants. However, designing an LAV with appropriate attenuation yet sufficient immunogenicity has proven challenging. In this study, we implemented reverse genetics to address these obstacles with a multifaceted LAV design that combined the codon deoptimization of genes for nonstructural proteins NS1 and NS2 (dNS), deletion of the small hydrophobic protein (ΔSH) gene, and replacement of the wild-type fusion (F) protein gene with a low-fusion RSV subgroup B F consensus sequence of the Buenos Aires clade (BAF). This vaccine candidate, RSV-A2-dNS-ΔSH-BAF (DB1), was attenuated in two models of primary human airway epithelial cells and in the upper and lower airways of cotton rats. DB1 was also highly immunogenic in cotton rats and elicited broadly neutralizing antibodies against a diverse panel of recombinant RSV strains. When vaccinated cotton rats were challenged with wild-type RSV A, DB1 reduced viral titers in the upper and lower airways by 3.8 log10 total PFU and 2.7 log10 PFU/g of tissue, respectively, compared to those in unvaccinated animals (P < 0.0001). DB1 was thus attenuated, highly immunogenic, and protective against RSV challenge in cotton rats. DB1 is the first RSV LAV to incorporate a low-fusion F protein as a strategy to attenuate viral replication and preserve immunogenicity. IMPORTANCE RSV is a leading cause of infant hospitalizations and deaths. The development of an effective vaccine for this high-risk population is therefore a public health priority. Although live-attenuated vaccines have been safely administered to RSV-naive infants, strategies to balance vaccine attenuation with immunogenicity have been elusive. In this study, we introduced a novel strategy to attenuate a recombinant RSV vaccine by incorporating a low-fusion, subgroup B F protein in the genetic background of codon-deoptimized nonstructural protein genes and a deleted small hydrophobic protein gene. The resultant vaccine candidate, DB1, was attenuated, highly immunogenic, and protective against RSV challenge in cotton rats. PMID:27279612

A Recombinant Respiratory Syncytial Virus Vaccine Candidate Attenuated by a Low-Fusion F Protein Is Immunogenic and Protective against Challenge in Cotton Rats.

PubMed

Rostad, Christina A; Stobart, Christopher C; Gilbert, Brian E; Pickles, Ray J; Hotard, Anne L; Meng, Jia; Blanco, Jorge C G; Moin, Syed M; Graham, Barney S; Piedra, Pedro A; Moore, Martin L

2016-08-15

Although respiratory syncytial virus (RSV) is the leading cause of lower respiratory tract infections in infants, a safe and effective vaccine is not yet available. Live-attenuated vaccines (LAVs) are the most advanced vaccine candidates in RSV-naive infants. However, designing an LAV with appropriate attenuation yet sufficient immunogenicity has proven challenging. In this study, we implemented reverse genetics to address these obstacles with a multifaceted LAV design that combined the codon deoptimization of genes for nonstructural proteins NS1 and NS2 (dNS), deletion of the small hydrophobic protein (ΔSH) gene, and replacement of the wild-type fusion (F) protein gene with a low-fusion RSV subgroup B F consensus sequence of the Buenos Aires clade (BAF). This vaccine candidate, RSV-A2-dNS-ΔSH-BAF (DB1), was attenuated in two models of primary human airway epithelial cells and in the upper and lower airways of cotton rats. DB1 was also highly immunogenic in cotton rats and elicited broadly neutralizing antibodies against a diverse panel of recombinant RSV strains. When vaccinated cotton rats were challenged with wild-type RSV A, DB1 reduced viral titers in the upper and lower airways by 3.8 log10 total PFU and 2.7 log10 PFU/g of tissue, respectively, compared to those in unvaccinated animals (P < 0.0001). DB1 was thus attenuated, highly immunogenic, and protective against RSV challenge in cotton rats. DB1 is the first RSV LAV to incorporate a low-fusion F protein as a strategy to attenuate viral replication and preserve immunogenicity. RSV is a leading cause of infant hospitalizations and deaths. The development of an effective vaccine for this high-risk population is therefore a public health priority. Although live-attenuated vaccines have been safely administered to RSV-naive infants, strategies to balance vaccine attenuation with immunogenicity have been elusive. In this study, we introduced a novel strategy to attenuate a recombinant RSV vaccine by incorporating a low-fusion, subgroup B F protein in the genetic background of codon-deoptimized nonstructural protein genes and a deleted small hydrophobic protein gene. The resultant vaccine candidate, DB1, was attenuated, highly immunogenic, and protective against RSV challenge in cotton rats. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

Hydrophobicity of 43 potting media: Its implications for raising seedlings in revegetation programs

NASA Astrophysics Data System (ADS)

Gautam, Resham; Ashwath, Nanjappa

2012-04-01

SummaryThe practice of using nursery-raised seedlings is becoming popular in revegetation programs, as this will allow rapid establishment of plants. However, this practice often results in low survival of seedlings in the field, especially in the tropics under rain fed conditions. Part of this can be attributed to hydrophobicity of the media being used in raising the seedlings. Hydrophobicity is the property of potting media which make the media not able to readily absorb water from the surrounding soil once the media dry out. Thus, 41 commercially available potting media and media components and two soil samples (Control) were assessed for hydrophobicity at different moisture levels via Water Droplet Penetration Test (WDPT). At the driest state (oven dried samples), the tested media were classified into five hydrophobicity classes, viz., extremely hydrophobic (WDP time >3600 s, 28% of the tested media), severely hydrophobic (WDP time 600-3600 s, 35%), strongly hydrophobic (WDP time 60-600 s, 21%), slightly hydrophobic (WDP time 5-60 s, 12%) and non-hydrophobic (WDP time <5 s, 5%). The test showed that hydrophobicity decreased with an increase in moisture content of the media. For example, when samples were oven dried, 63% of the media were found severely to extremely hydrophobic whereas only 14% of the media remained in these categories when moisture content increased to 15%. Significant (P < 0.05) negative correlation was observed between hydrophobicity and pH (R2 = 0.92), and hydrophobicity and water holding capacity (P < 0.05) of the media (R2 = 0.89). However, no significant correlation was observed between hydrophobicity to electrical conductivity of the media (R2 = 0.03). The media wettability (ratio of hydrophilic and hydrophobic functional group of organic matter) as determined by FTIR spectroscopy was significantly (P < 0.001) higher in non-hydrophobic media than in hydrophobic media. Most Probable Number (MPN) adapted from a "Sheen Screen" method suggested that the number of wax degrading bacteria were similar amongst the non-hydrophobic and hydrophobic media. This indicates that the bacterial number may not be an important factor for breaking down hydrophobicity but most likely it is the bacterial activity that plays an important role in this process. Since the majority of the tested potting media were hydrophobic in nature (under dry conditions), and hydrophobicity affects survival of seedlings in the field, we recommend testing of potting media for hydrophobicity as a complimentary requirement of the Australian Standards. Studies should also be undertaken to identify the constituents of potting media that are responsible for imparting hydrophobicity to the media, and to identify treatments (e.g., lime or detergents or surfactants) that would help minimise hydrophobicity in the potting media.

Efficient dynamic molecular simulation using QSAR model to know inhibition activity in breast cancer medicine

NASA Astrophysics Data System (ADS)

Zharifah, A.; Kusumowardani, E.; Saputro, A.; Sarwinda, D.

2017-07-01

According to data from GLOBOCAN (IARC) at 2012, breast cancer was the highest rated of new cancer case by 43.3 % (after controlled by age), with mortality rated as high as 12.9 %. Oncology is a major field which focusing on improving the development of drug and therapeutics cancer in pharmaceutical and biotechnology companies. Nowadays, many researchers lead to computational chemistry and bioinformatic for pharmacophore generation. A pharmacophore describes as a group of atoms in the molecule which is considered to be responsible for a pharmacological action. Prediction of biological function from chemical structure in silico modeling reduces the use of chemical reagents so the risk of environmental pollution decreased. In this research, we proposed QSAR model to analyze the composition of cancer drugs which assumed to be homogenous in character and treatment. Atomic interactions which analyzed are learned through parameters such as log p as descriptors hydrophobic, n_poinas descriptor contour strength and molecular structure, and also various concentrations inhibitor (micromolar and nanomolar) from NCBI drugs bank. The differences inhibitor activity was observed by the presence of IC 50 residues value from inhibitor substances at various concentration. Then, we got a general overview of the state of safety for drug stability seen from its IC 50 value. In our study, we also compared between micromolar and nanomolar inhibitor effect from QSAR model results. The QSAR model analysis shows that the drug concentration with nanomolar is better than micromolar, related with the content of inhibitor substances concentration. This QSAR model got the equation: Log 1/IC50 = (0.284) (±0.195) logP + (0.02) (±0.012) n_poin + (-0.005) (±0.083) Inhibition10.2nanoM + (0.1) (±0.079) Inhibition30.5nanoM + (-0.016) (±0.045) Inhibition91.5nanoM + (-2.572) (±1.570) (n = 13; r = 0.813; r2 = 0.660; s = 0.764; F = 2.720; q2 = 0.660).

Critical Synergistic Concentration of Lecithin Phospholipids Improves the Antimicrobial Activity of Eugenol against Escherichia coli

PubMed Central

Zhang, Haoshu; Dudley, Edward G.

2017-01-01

ABSTRACT In this study, the effect of individual lecithin phospholipids on the antimicrobial properties of eugenol against Escherichia coli C600 was investigated. We tested five major phospholipids common in soy or egg lecithin (1,2-dihexadecanoyl-sn-glycero-3-phosphocholine [DPPC], 1,2-dioctadecanoyl-sn-glycero-3-phosphocholine [DSPC], 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine [DPPE], 1,2-dihexadecanoyl-sn-glycero-3-phosphate [sodium salt] [DPPA], and 1,2-dihexadecanoyl-sn-glycero-3-phospho-l-serine [DPPS]) and one synthetic cationic phospholipid (1,2-dioctadecanoyl-sn-glycero-3-ethylphosphocholine [18:0 EPC]). Among the six phospholipids, DPPC, DSPC, DPPE, DPPA, and the cationic 18:0 EPC showed critical synergistic concentrations that significantly improved the inactivation effect of eugenol against E. coli after 30 min of exposure. At the critical synergistic concentration, an additional ca. 0.4 to 1.9 log reduction (ca. 0.66 to 2.17 log CFU/ml reduction) in the microbial population was observed compared to eugenol-only (control) treatments (ca. 0.25 log reduction). In all cases, increasing the phospholipid amount above the critical synergistic concentration (which was different for each phospholipid) resulted in antimicrobial properties similar to those seen with the eugenol-only (control) treatments. DPPS did not affect the antimicrobial properties of eugenol at the tested concentrations. The critical synergistic concentration of phospholipids was correlated with their critical micelle concentrations (CMC). IMPORTANCE Essential oils (EOs) are naturally occurring antimicrobials, with limited use in food due to their hydrophobicity and strong aroma. Lecithin is used as a natural emulsifier to stabilize EOs in aqueous systems. We previously demonstrated that, within a narrow critical-concentration window, lecithin can synergistically enhance the antimicrobial properties of eugenol. Since lecithin is a mixture of different phospholipids, we aimed to identify which phospholipids are crucial for the observed synergistic effect. This research studied the bioactivity of lecithin phospholipids, contributing to a rational design in using lecithin to effectively control foodborne pathogens in foods. PMID:28842540

Drug-like density: a method of quantifying the "bindability" of a protein target based on a very large set of pockets and drug-like ligands from the Protein Data Bank.

PubMed

Sheridan, Robert P; Maiorov, Vladimir N; Holloway, M Katharine; Cornell, Wendy D; Gao, Ying-Duo

2010-11-22

One approach to estimating the "chemical tractability" of a candidate protein target where we know the atomic resolution structure is to examine the physical properties of potential binding sites. A number of other workers have addressed this issue. We characterize ~290,000 "pockets" from ~42,000 protein crystal structures in terms of a three parameter "pocket space": volume, buriedness, and hydrophobicity. A metric DLID (drug-like density) measures how likely a pocket is to bind a drug-like molecule. This is calculated from the count of other pockets in its local neighborhood in pocket space that contain drug-like cocrystallized ligands and the count of total pockets in the neighborhood. Surprisingly, despite being defined locally, a global trend in DLID can be predicted by a simple linear regression on log(volume), buriedness, and hydrophobicity. Two levels of simplification are necessary to relate the DLID of individual pockets to "targets": taking the best DLID per Protein Data Bank (PDB) entry (because any given crystal structure can have many pockets), and taking the median DLID over all PDB entries for the same target (because different crystal structures of the same protein can vary because of artifacts and real conformational changes). We can show that median DLIDs for targets that are detectably homologous in sequence are reasonably similar and that median DLIDs correlate with the "druggability" estimate of Cheng et al. (Nature Biotechnology 2007, 25, 71-75).

Potential for biodegradation and sorption of acetaminophen, caffeine, propranolol and acebutolol in lab-scale aqueous environments.

PubMed

Lin, Angela Yu-Chen; Lin, Chih-Ann; Tung, Hsin-Hsin; Chary, N Sridhara

2010-11-15

Sorption and combined sorption-biodegradation experiments were conducted in laboratory batch studies with 100 g soil/sediments and 500 mL water to investigate the fates in aqueous environments of acetaminophen, caffeine, propranolol, and acebutolol, four frequently used and often-detected pharmaceuticals. All four compounds have demonstrated significant potential for degradation and sorption in natural aqueous systems. For acetaminophen, biodegradation was found to be a primary mechanism for degradation, with a half-life (t(1/2)) for combined sorption-biodegradation of 2.1 days; in contrast, sorption alone was responsible only for a 30% loss of aqueous-phase acetaminophen after 15 days. For caffeine, both biodegradation and sorption were important (t(1/2) for combined sorption-biodegradation was 1.5 days). However, for propranolol and acebutolol, sorption was found to be the most significant removal mechanism and was not affected by biodegradation. Desorption experiments revealed that the sorption process was mostly irreversible. High values were found for K(d) for caffeine, propranolol, and acebutolol, ranging from 250 to 1900 L kg(-1), which explained their greater tendency for sorption onto sediments, compared to the more hydrophilic acetaminophen. Experimentally derived values for logK(oc) differed markedly from values calculated from correlation equations. This discrepancy was attributed to the fact that these equations are well suited for hydrophobic interactions but may fail to predict the sorption of polar and ionic compounds. These results suggest that mechanisms other than hydrophobic interactions played an important role in the sorption process. Copyright © 2010 Elsevier B.V. All rights reserved.

Risk Characterization for Future Training Scenarios at the Massachusetts Military Reservation (MMR), Final Results

DTIC Science & Technology

2005-08-01

1979) 0.63d ocK f= owK (1) where Kow = octanol to water partitioning coefficient, L/kg foc = fraction of organic carbon of the soil Barber...Software 59 2-Methylthiophene 554-14-3 0.135 EPI Software 60 2-Nitrophenol 88-75-5 0.039 EPI Software 61 2- Octanone 111-13-7 0.148 EPI Software 62 2...Nitrophenol 88-75-5 6.09E-09 1.72E-12 2- Octanone 111-13-7 2.56E-11 7.23E-15 2-Pentanone 107-87-9 1.83E-08 5.18E-12 2-Propanol 67-63-0 4.08E-09 1.15E-12 2

Evaluation of Antimicrobial Efficiency of New Polymers Comprised by Covalently Attached and/or Electrostatically Bound Bacteriostatic Species, Based on Quaternary Ammonium Compounds.

PubMed

Kougia, Efstathia; Tselepi, Maria; Vasilopoulos, Gavriil; Lainioti, Georgia Ch; Koromilas, Nikos D; Druvari, Denisa; Bokias, Georgios; Vantarakis, Apostolos; Kallitsis, Joannis K

2015-12-01

In the present work a detailed study of new bacteriostatic copolymers with quaternized ammonium groups introduced in the polymer chain through covalent attachment or electrostatic interaction, was performed. Different copolymers have been considered since beside the active species, the hydrophobic/hydrophilic nature of the co-monomer was also evaluated in the case of covalently attached bacteriostatic groups, aiming at achieving permanent antibacterial activity. Homopolymers with quaternized ammonium/phosphonium groups were also tested for comparison reasons. The antimicrobial activity of the synthesized polymers after 3 and 24 h of exposure at 4 and 22 °C was investigated on cultures of Gram-negative (P. aeruginosa, E. coli) and Gram-positive (S. aureus, E. faecalis) bacteria. It was found that the combination of the hydrophilic monomer acrylic acid (AA), at low contents, with the covalently attached bacteriostatic group vinyl benzyl dimethylhexadecylammonium chloride (VBCHAM) in the copolymer P(AA-co-VBCHAM88), resulted in a high bacteriostatic activity against P. aeruginosa and E. faecalis (6 log reduction in certain cases). Moreover, the combination of covalently attached VBCHAM units with electrostatically bound cetyltrimethylammonium 4-styrene sulfonate (SSAmC16) units in the P(SSAmC16-co-VBCHAMx) copolymers led to efficient antimicrobial materials, especially against Gram-positive bacteria, where a log reduction between 4.9 and 6.2 was verified. These materials remain remarkably efficient even when they are incorporated in polysulfone membranes.

Binding of dicamba to soluble and bound extracellular polymeric substances (EPS) from aerobic activated sludge: a fluorescence quenching study.

PubMed

Pan, Xiangliang; Liu, Jing; Zhang, Daoyong; Chen, Xi; Song, Wenjuan; Wu, Fengchang

2010-05-15

Binding of dicamba to soluble EPS (SEPS) and bound EPS (BEPS) from aerobic activated sludge was investigated using fluorescence spectroscopy. Two protein-like fluorescence peaks (peak A with Ex/Em=225 nm/342-344 nm and peak B with Ex/Em=275/340-344 nm) were identified in SEPS and BEPS. Humic-like fluorescence peak C (Ex/Em=270-275 nm/450-460 nm) was only found in BEPS. Fluorescence of the peaks A and B for SEPS and peak A for BEPS were markedly quenched by dicamba at all temperatures whereas fluorescence of peaks B and C for BEPS was quenched only at 298 K. A dynamic process dominated the fluorescence quenching of peak A of both SEPS and BEPS. Fluorescence quenching of peak B and C was governed a static process. The effective quenching constants (logK(a)) were 4.725-5.293 for protein-like fluorophores of SEPS and 4.23-5.190 for protein-like fluorophores of BEPS, respectively. LogK(a) for humic-like substances was 3.85. Generally, SEPS had greater binding capacity for dicamba than BEPS, and protein-like substances bound dicamba more strongly than humic-like substances. Binding of dicamba to SEPS and BEPS was spontaneous and exothermic. Electrostatic force and hydrophobic interaction forces play a crucial role in binding of dicamba to EPS. Copyright © 2010 Elsevier Inc. All rights reserved.

Microbiological evaluation of groups of beef carcasses: heifers and steers.

PubMed Central

Jericho, K W; Bradley, J A; Kozub, G C

1994-01-01

Numbers of mesophilic bacteria were estimated on carcasses of 25 heifers and 25 steers of beef breeds in a modern, high-line-speed abattoir. One side of each carcass from each sex was sampled at the end of the kill-floor, before the carcass wash, on each of 25 visits. Two adjacent excision samples (5 x 5 x 0.5 cm) were taken from each of ten sites and processed for automatic enumeration of aerobic bacteria on hydrophobic grid membrane filters. The effects of sex and carcass weight on bacterial counts were examined. Groups of carcasses were examined to determine the sample size required for future assessments of kill-floor hygiene. The log10 of the most probable number of growth units (MPNGU)/cm2 did not differ significantly between heifers and steers (average over the ten sites of 2.2) and there was no effect of carcass weight on bacterial counts for nine of the ten sites. There were, however, highly significant (p < 0.001) differences in the counts between sites and the counts from the ten sites clustered into five homogenous groups. The between-carcass component of variation at a site was generally larger than the within-carcass component. We conclude that, to estimate the mean log10 MPNGU/cm2 at a site to within +/- 0.5 units, future group-carcass evaluations require about 200 samples from 10 (two adjacent samples/site) or 20 carcasses (one sample/site). PMID:7954120

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.

Super-hydrophobic yolk-shell nanostructure with enhanced catalytic performance in the reduction of hydrophobic nitroaromatic compounds.

PubMed

Shi, Song; Wang, Min; Chen, Chen; Gao, Jin; Ma, Hong; Ma, Jiping; Xu, Jie

2013-10-25

A self-templating method to fabricate a super-hydrophobic yolk-shell nano-reactor was reported. Metal nanoparticles were encapsulated in the porous super-hydrophobic shell. This super-hydrophobic catalyst showed excellent performance in the reduction of nitroaromatic compounds in aqueous phase and a positive correlation was found between the reaction rate and the hydrophobicity of the substrate.

The Hydrophobic Effect.

ERIC Educational Resources Information Center

Huque, Entazul M.

1989-01-01

Discusses the physical basis and current understanding of hydrophobic effects. The thermodynamic background of the effects, hydrophobic hydration, and hydrophobic interactions are described. Four existing controversies are outlined. (YP)

Determination of steroid sex hormones in water and urine matrices by stir bar sorptive extraction and liquid chromatography with diode array detection.

PubMed

Almeida, C; Nogueira, J M F

2006-06-16

In this study, stir bar sorptive extraction and liquid desorption followed by high performance liquid chromatography with diode array detection (SBSE-LD-HPLC/DAD) were combined for the simultaneous determination of nine steroid sex hormones (estrone, 17alpha-estradiol, 17beta-estradiol, 17alpha-ethynylestradiol, diethylstilbestrol, mestranol, progesterone, 19-norethisterone and norgestrel) in water and urine matrices. During the method development, it has been demonstrated that equilibrium time, ionic strength and back extraction solvents are the most important parameters to control, for determining the nine-hormones in water matrices, in which stir bars coated with 126 microl of polydimethylsiloxane were used. Assays performed on 30 ml water samples spiked at 10 microg/l levels under optimised experimental conditions, yielded recoveries ranging from 11.1+/-4.9% (17beta-estradiol) to 100.2+/-10.4% (mestranol), showed that the methodology is well described by the octanol-water partition coefficients (K(PDMS/W) approximately K(O/W)) for the latter, while pronounced deviations to the theoretical efficiency (K(PDMS/W) not equal K(O/W)) were observed for the remaining hormones. From calibration studies, a good analytical performance for all hormones was attained, including a suitable precision (2.1-17.1%), low limits of detection (0.3-1.0 microg/l) and an excellent linear dynamic range (1.25-50.0 microg/l). Assays on environmental water and urine matrices showed recovery yields in worthy good agreement with the spiking level (10 microg/l), and suitability for profiling low microg/l levels of natural hormones in urine samples taken from pregnant women. The present methodology is easy, reliable and sensitive at the trace level, only requiring a low sample volume, showing to be a good analytical alternative to routine quality control for environmental and biomedical laboratories.

Screening-level models to estimate partition ratios of organic chemicals between polymeric materials, air and water.

PubMed

Reppas-Chrysovitsinos, Efstathios; Sobek, Anna; MacLeod, Matthew

2016-06-15

Polymeric materials flowing through the technosphere are repositories of organic chemicals throughout their life cycle. Equilibrium partition ratios of organic chemicals between these materials and air (KMA) or water (KMW) are required for models of fate and transport, high-throughput exposure assessment and passive sampling. KMA and KMW have been measured for a growing number of chemical/material combinations, but significant data gaps still exist. We assembled a database of 363 KMA and 910 KMW measurements for 446 individual compounds and nearly 40 individual polymers and biopolymers, collected from 29 studies. We used the EPI Suite and ABSOLV software packages to estimate physicochemical properties of the compounds and we employed an empirical correlation based on Trouton's rule to adjust the measured KMA and KMW values to a standard reference temperature of 298 K. Then, we used a thermodynamic triangle with Henry's law constant to calculate a complete set of 1273 KMA and KMW values. Using simple linear regression, we developed a suite of single parameter linear free energy relationship (spLFER) models to estimate KMA from the EPI Suite-estimated octanol-air partition ratio (KOA) and KMW from the EPI Suite-estimated octanol-water (KOW) partition ratio. Similarly, using multiple linear regression, we developed a set of polyparameter linear free energy relationship (ppLFER) models to estimate KMA and KMW from ABSOLV-estimated Abraham solvation parameters. We explored the two LFER approaches to investigate (1) their performance in estimating partition ratios, and (2) uncertainties associated with treating all different polymers as a single "bulk" polymeric material compartment. The models we have developed are suitable for screening assessments of the tendency for organic chemicals to be emitted from materials, and for use in multimedia models of the fate of organic chemicals in the indoor environment. In screening applications we recommend that KMA and KMW be modeled as 0.06 ×KOA and 0.06 ×KOW respectively, with an uncertainty range of a factor of 15.

Chlorine resistant desalination membranes based on directly sulfonated poly(arylene ether sulfone) copolymers

DOEpatents

McGrath, James E [Blacksburg, VA; Park, Ho Bum [Austin, TX; Freeman, Benny D [Austin, TX

2011-10-04

The present invention provides a membrane, kit, and method of making a hydrophilic-hydrophobic random copolymer membrane. The hydrophilic-hydrophobic random copolymer membrane includes a hydrophilic-hydrophobic random copolymer. The hydrophilic-hydrophobic random copolymer includes one or more hydrophilic monomers having a sulfonated polyarylsulfone monomer and a second monomer and one or more hydrophobic monomers having a non-sulfonated third monomer and a fourth monomer. The sulfonated polyarylsulfone monomer introduces a sulfonate into the hydrophilic-hydrophobic random copolymer prior to polymerization.

Optimal Hydrophobicity in Ring-Opening Metathesis Polymerization-Based Protein Mimics Required for siRNA Internalization.

PubMed

deRonde, Brittany M; Posey, Nicholas D; Otter, Ronja; Caffrey, Leah M; Minter, Lisa M; Tew, Gregory N

2016-06-13

Exploring the role of polymer structure for the internalization of biologically relevant cargo, specifically siRNA, is of critical importance to the development of improved delivery reagents. Herein, we report guanidinium-rich protein transduction domain mimics (PTDMs) based on a ring-opening metathesis polymerization scaffold containing tunable hydrophobic moieties that promote siRNA internalization. Structure-activity relationships using Jurkat T cells and HeLa cells were explored to determine how the length of the hydrophobic block and the hydrophobic side chain compositions of these PTDMs impacted siRNA internalization. To explore the hydrophobic block length, two different series of diblock copolymers were synthesized: one series with symmetric block lengths and one with asymmetric block lengths. At similar cationic block lengths, asymmetric and symmetric PTDMs promoted siRNA internalization in the same percentages of the cell population regardless of the hydrophobic block length; however, with 20 repeat units of cationic charge, the asymmetric block length had greater siRNA internalization, highlighting the nontrivial relationships between hydrophobicity and overall cationic charge. To further probe how the hydrophobic side chains impacted siRNA internalization, an additional series of asymmetric PTDMs was synthesized that featured a fixed hydrophobic block length of five repeat units that contained either dimethyl (dMe), methyl phenyl (MePh), or diphenyl (dPh) side chains and varied cationic block lengths. This series was further expanded to incorporate hydrophobic blocks consisting of diethyl (dEt), diisobutyl (diBu), and dicyclohexyl (dCy) based repeat units to better define the hydrophobic window for which our PTDMs had optimal activity. High-performance liquid chromatography retention times quantified the relative hydrophobicities of the noncationic building blocks. PTDMs containing the MePh, diBu, and dPh hydrophobic blocks were shown to have superior siRNA internalization capabilities compared to their more and less hydrophobic counterparts, demonstrating a critical window of relative hydrophobicity for optimal internalization. This better understanding of how hydrophobicity impacts PTDM-induced internalization efficiencies will help guide the development of future delivery reagents.

Lactic acid bacteria in Hamei and Marcha of North East India.

PubMed

Tamang, J P; Dewan, S; Tamang, B; Rai, A; Schillinger, U; Holzapfel, W H

2007-06-01

Hamei and Marcha are mixed dough inocula used as starters for preparation of various indigenous alcoholic beverages in Manipur and Sikkim in India, respectively. These starters are traditionally prepared from rice with wild herbs and spices. Samples of Hamei and Marcha, collected from Manipur and Sikkim, respectively, were analysed for lactic acid bacterial composition. The population of lactic acid bacteria (LAB) was 6.9 and 7.1 Log cfu/g in Hamei and Marcha, respectively. On the basis of phenotypic and genotypic characters, LAB strains isolated from Hamei and Marcha were identified as Pediococcus pentosaceus, Lactobacillus plantarum and Lactobacillus brevis. Technological properties of LAB such as antimicrobial properties, effect on acidification, ability to produce biogenic amines and ethanol, degree of hydrophobicity and enzymatic activities were also performed. Pediococcus pentosaceus HS: B1, isolated from Hamei, was found to produce bacteriocin. None of the strains produced biogenic amines. LAB strains showed a strong acidifying ability and they also produced a wide spectrum of enzymes.

Removal and fate of micropollutants in a sponge-based moving bed bioreactor.

PubMed

Luo, Yunlong; Guo, Wenshan; Ngo, Huu Hao; Nghiem, Long Duc; Hai, Faisal Ibney; Kang, Jinguo; Xia, Siqing; Zhang, Zhiqiang; Price, William Evan

2014-05-01

This study investigated the removal of micropollutants using polyurethane sponge as attached-growth carrier. Batch experiments demonstrated that micropollutants could adsorb to non-acclimatized sponge cubes to varying extents. Acclimatized sponge showed significantly enhanced removal of some less hydrophobic compounds (log D<2.5), such as ibuprofen, acetaminophen, naproxen, and estriol, as compared with non-acclimatized sponge. The results for bench-scale sponge-based moving bed bioreactor (MBBR) system elucidated compound-specific variation in removal, ranging from 25.9% (carbamazepine) to 96.8% (β-Estradiol 17-acetate) on average. In the MBBR system, biodegradation served as a major removal pathway for most compounds. However, sorption to sludge phase was also a notable removal mechanism of some persistent micropollutants. Particularly, carbamazepine, ketoprofen and pentachlorophenol were found at high concentrations (7.87, 6.05 and 5.55 μg/g, respectively) on suspended biosolids. As a whole, the effectiveness of MBBR for micropollutant removal was comparable with those of activated sludge processes and MBRs. Copyright © 2014 Elsevier Ltd. All rights reserved.

Mechanisms underlying changes in indomethacin solubility with local anesthetics and related basic additives

NASA Astrophysics Data System (ADS)

Shimada, Yohsuke; Tateuchi, Ryo; Chatani, Hitoshi; Goto, Satoru

2018-03-01

Indomethacin (IND), an acidic nonsteroidal anti-inflammatory drug, and lidocaine (LID), a local anesthetic (LA), form a eutectic complex when mixed, with a lower melting point. The aqueous solubility of the mixture is greater than that of IND or LID alone, improving the bioavailability of IND. Therefore, IND and LID can be used to model changes in efficacy caused by physicochemical interactions between drugs. In this study, the intermolecular interactions between IND and structurally similar LAs were examined by measuring solubility and analyzing thermodynamics using differential scanning calorimetry. The results indicate that the solubility of IND (log S'IND) varies with LA hydrophobicity. Reductions in melting point resulting from mixing IND and LAs contributed to changes in IND solubility, attributable to direct intermolecular interactions between IND and the LAs. In addition, binding energy of IND-LA as in water was calculated, and the values were correlating with the solubility of IND in experiments. Understanding these interactions will help address some of the problems encountered in polypharmacy.

Solubility, ionization, and partitioning behavior of unsymmetrical disulfide compounds: alkyl 2-imidazolyl disulfides.

PubMed

Hashash, Ahmad; Kirkpatrick, D Lynn; Lazo, John S; Block, Lawrence H

2002-07-01

Alkyl 2-imidazolyl disulfide compounds are novel antitumor agents, one of which is currently being evaluated in Phase I clinical trials. These molecules contain an unsymmetrical disulfide fragment, the lipophilic and electronic contributions of which are still not defined in the literature. Lipophilicity, ionization, and solubility of a number of alkyl 2-imidazolyl disulfides were studied. Based on the additivity of lipophilicity and ionization properties, the contribution of the unsymmetrical disulfide fragment to lipophilicity and ionization was elucidated. The unsymmetrical disulfide fragment contributed a Rekker's hydrophobic constant of 0.761 to the lipophilicity of these compounds and an approximated Hammett constant (sigma) of 0.30 to their ionization. The applicability of the general solubility equation (GSE) proposed by Jain and Yalkowsky in predicting the aqueous solubility of these analogs was evaluated. The GSE correctly ranked the aqueous solubilities of these compounds and estimated their log molar solubilities with an average absolute error of 0.35. Copyright 2002 Wiley-Liss Inc.

Modelling the fate of micropollutants in the marine environment using passive sampling.

PubMed

Claessens, Michiel; De Laender, Frederik; Monteyne, Els; Roose, Patrick; Janssen, Colin R

2015-07-15

Polydimethylsiloxane sheets were used to determine freely dissolved concentrations (C(diss)) of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) in the Belgian coastal zone. Equilibrium models were used to predict the whole water concentrations (C(ww)) of these compounds as well as their concentrations in sediment, suspended particulate matter (SPM) and biota. In general, contaminant concentrations were predicted well for whole water and biota. C(ww) was increasingly underpredicted as K(oc) increased, possibly because of the presence of black carbon. Concentrations in biota were overestimated by the equilibrium approach when logK(ow) exceeded 6.5, suggesting an increasing role of transformation processes. Concentrations of PAHs and PCBs in sediment and SPM were consistently underpredicted although a good correlation between measured and predicted values was observed. This was potentially due to the use of experimental K(oc) values which have been found to underestimate partitioning of hydrophobic substances to sediment in field studies. Copyright © 2015 Elsevier Ltd. All rights reserved.

In vitro penetration through the skin layers of topically applied glucocorticoids.

PubMed

Carrer, Victor; Alonso, Cristina; Oliver, Marc Adrià; Coderch, Luisa

2018-05-22

Corticoids are actives widely used in the treatment of skin diseases. This work aims to study the penetration of three corticoids (betamethasone, clobetasol and flurandrenolide), their relationship with their Log D values and the effects of the vehicles. The three compounds were applied on a Franz-type diffusion cell in propylene glycol solution and their respective commercial creams and ointments. The active amounts found in the stratum corneum, epidermal and dermal layers of the skin were investigated. Their diffusions were greatly affected by the formulation, moreover higher amounts of substance in the epidermis and dermis were detected in ointments than in creams. The enhancement effect of propylene glycol was also observed. Moreover, the differences between the three substances could be related to their lipophilicity, molecular structure and molecular weight. The more hydrophobic compounds (clobetasol and betamethasone) are present in higher amounts in the epidermis and dermis, while the hydrophilic compound (flurandrenolide) is mostly present in the receptor fluid. This article is protected by copyright. All rights reserved.

Signature of hydrophobic hydration in a single polymer

PubMed Central

Li, Isaac T. S.; Walker, Gilbert C.

2011-01-01

Hydrophobicity underpins self-assembly in many natural and synthetic molecular and nanoscale systems. A signature of hydrophobicity is its temperature dependence. The first experimental evaluation of the temperature and size dependence of hydration free energy in a single hydrophobic polymer is reported, which tests key assumptions in models of hydrophobic interactions in protein folding. Herein, the hydration free energy required to extend three hydrophobic polymers with differently sized aromatic side chains was directly measured by single molecule force spectroscopy. The results are threefold. First, the hydration free energy per monomer is found to be strongly dependent on temperature and does not follow interfacial thermodynamics. Second, the temperature dependence profiles are distinct among the three hydrophobic polymers as a result of a hydrophobic size effect at the subnanometer scale. Third, the hydration free energy of a monomer on a macromolecule is different from a free monomer; corrections for the reduced hydration free energy due to hydrophobic interaction from neighboring units are required. PMID:21911397

Simulating the minimum core for hydrophobic collapse in globular proteins.

PubMed Central

Tsai, J.; Gerstein, M.; Levitt, M.

1997-01-01

To investigate the nature of hydrophobic collapse considered to be the driving force in protein folding, we have simulated aqueous solutions of two model hydrophobic solutes, methane and isobutylene. Using a novel methodology for determining contacts, we can precisely follow hydrophobic aggregation as it proceeds through three stages: dispersed, transition, and collapsed. Theoretical modeling of the cluster formation observed by simulation indicates that this aggregation is cooperative and that the simulations favor the formation of a single cluster midway through the transition stage. This defines a minimum solute hydrophobic core volume. We compare this with protein hydrophobic core volumes determined from solved crystal structures. Our analysis shows that the solute core volume roughly estimates the minimum core size required for independent hydrophobic stabilization of a protein and defines a limiting concentration of nonpolar residues that can cause hydrophobic collapse. These results suggest that the physical forces driving aggregation of hydrophobic molecules in water is indeed responsible for protein folding. PMID:9416609

Robust Hydrophobic Surfaces from Suspension HVOF Thermal Sprayed Rare-Earth Oxide Ceramics Coatings.

PubMed

Bai, M; Kazi, H; Zhang, X; Liu, J; Hussain, T

2018-05-03

This study has presented an efficient coating method, namely suspension high velocity oxy-fuel (SHVOF) thermal spraying, to produce large super-hydrophobic ceramic surfaces with a unique micro- and nano-scale hierarchical structures to mimic natural super-hydrophobic surfaces. CeO 2 was selected as coatings material, one of a group of rare-earth oxide (REO) ceramics that have recently been found to exhibit intrinsic hydrophobicity, even after exposure to high temperatures and abrasive wear. Robust hydrophobic REO ceramic surfaces were obtained from the deposition of thin CeO 2 coatings (3-5 μm) using an aqueous suspension with a solid concentration of 30 wt.% sub-micron CeO 2 particles (50-200 nm) on a selection of metallic substrates. It was found that the coatings' hydrophobicity, microstructure, surface morphology, and deposition efficiency were all determined by the metallic substrates underneath. More importantly, it was demonstrated that the near super-hydrophobicity of SHVOF sprayed CeO 2 coatings was achieved not only by the intrinsic hydrophobicity of REO but also their unique hierarchically structure. In addition, the coatings' surface hydrophobicity was sensitive to the O/Ce ratio, which could explain the 'delayed' hydrophobicity of REO coatings.

Dewetting and Hydrophobic Interaction in Physical and Biological Systems

PubMed Central

Berne, Bruce J.; Weeks, John D.; Zhou, Ruhong

2013-01-01

Hydrophobicity manifests itself differently on large and small length scales. This review focuses on large length scale hydrophobicity, particularly on dewetting at single hydrophobic surfaces and drying in regions bounded on two or more sides by hydrophobic surfaces. We review applicable theories, simulations and experiments pertaining to large scale hydrophobicity in physical and biomoleclar systems and clarify some of the critical issues pertaining to this subject. Given space constraints, we could not review all of the significant and interesting work in this very active field. PMID:18928403

Recent experimental advances on hydrophobic interactions at solid/water and fluid/water interfaces.

PubMed

Zeng, Hongbo; Shi, Chen; Huang, Jun; Li, Lin; Liu, Guangyi; Zhong, Hong

2015-03-15

Hydrophobic effects play important roles in a wide range of natural phenomena and engineering processes such as coalescence of oil droplets in water, air flotation of mineral particles, and folding and assembly of proteins and biomembranes. In this work, the authors highlight recent experimental attempts to reveal the physical origin of hydrophobic effects by directly quantifying the hydrophobic interaction on both solid/water and fluid/water interfaces using state-of-art nanomechanical techniques such as surface forces apparatus and atomic force microscopy (AFM). For solid hydrophobic surfaces of different hydrophobicity, the range of hydrophobic interaction was reported to vary from ∼10 to >100 nm. With various characterization techniques, the very long-ranged attraction (>100 nm) has been demonstrated to be mainly attributed to nonhydrophobic interaction mechanisms such as pre-existing nanobubbles and molecular rearrangement. By ruling out these factors, intrinsic hydrophobic interaction was measured to follow an exponential law with decay length of 1-2 nm with effective range less than 20 nm. On the other hand, hydrophobic interaction measured at fluid interfaces using AFM droplet/bubble probe technique was found to decay with a much shorter length of ∼0.3 nm. This discrepancy of measured decay lengths is proposed to be attributed to inherent physical distinction between solid and fluid interfaces, which impacts the structure of interface-adjacent water molecules. Direct measurement of hydrophobic interaction on a broader range of interfaces and characterization of interfacial water molecular structure using spectroscopic techniques are anticipated to help unravel the origin of this rigidity-related mismatch of hydrophobic interaction and hold promise to uncover the physical nature of hydrophobic effects. With improved understanding of hydrophobic interaction, intrinsic interaction mechanisms of many biological and chemical pathways can be better elucidated, and novel devices/processes can be developed with capacity to modulate and control the hydrophobic effects from the molecular to the macroscopic scale.

Sorptive capacity of membrane lipids, storage lipids, and proteins: a preliminary study of partitioning of organochlorines in lean fish from a PCB-contaminated freshwater lake.

PubMed

Mäenpää, Kimmo; Leppänen, Matti T; Figueiredo, Kaisa; Tigistu-Sahle, Feven; Käkelä, Reijo

2015-01-01

Knowledge on the internal distribution of halogenated organic chemicals (HOCs) would improve our understanding of dose-effect relationships and subsequently improve risk assessment of contaminated sites. Herein, we determine the concentrations of HOCs based on equilibrium partitioning in storage lipids, membrane lipids, and proteins in field-contaminated fish using equilibrium sampling devices. The study shows the importance of protein as a sorptive phase in lean fish. Our results provide a basis for using species-specific equilibrium partitioning coefficients between sorptive tissues and fish internal water as a substitute for K(ow) in, for example, upgrading models that simulate food-chain accumulation of the chemical.

Defining the minimum size of a hydrophobic cluster in two-stranded α-helical coiled-coils: Effects on protein stability

PubMed Central

Lu, Stephen M.; Hodges, Robert S.

2004-01-01

The α-helical coiled-coil motif is characterized by a heptad repeat pattern (abcdefg)n in which residues a and d form the hydrophobic core. Long coiled-coils (e.g., tropomyosin, 284 residues per polypeptide chain) typically do not have a continuous hydrophobic core of stabilizing residues, but rather one that consists of alternating clusters of stabilizing and destabilizing residues. We have arbitrarily defined a cluster as a minimum of three consecutive stabilizing or destabilizing residues in the hydrophobic core. We report here on a series of two-stranded, disulfide-bridged parallel α-helical coiled-coils that contain a central cassette of three consecutive hydrophobic core positions (d, a, and d) with a destabilizing cluster of three consecutive Ala residues in the hydrophobic core on each side of the cassette. The effect of adding one to three stabilizing hydrophobes in these positions (Leu or Ile; denoted as •) was investigated. Alanine residues (denoted as ○) are used to represent destabilizing residues. The peptide with three Ala residues in the d a d cassette positions (○○○) was among the least stable coiled-coil (Tm = 39.3°C and Urea1/2 = 1.9 M). Surprisingly, the addition of one stabilizing hydrophobe (Leu) to the cassette or two stabilizing hydrophobes (Leu), still interspersed by an Ala in the cassette (•○•), also did not lead to any gain in stability. However, peptides with two adjacent hydrophobes in the cassette (••○)(○••) did show a gain in stability of 0.9 kcal/mole over the peptide with two interspersed hydrophobes (•○•). Because the latter three peptides have the same inherent hydrophobicity, the juxtaposition of stabilizing hydrophobes leads to a synergistic effect, and thus a clustering effect. The addition of a third stabilizing hydrophobe to the cassette (•••) resulted in a further synergistic gain in stability of 1.7 kcal/mole (Tm = 54.1°C and Urea1/2 = 3.3M). Therefore, the role of hydrophobicity in the hydrophobic core of coiled-coils is extremely context dependent and clustering is an important aspect of protein folding and stability. PMID:14978309

[Comparison of four MICS intraocular lenses regarding their rates of neodymium:YAG laser capsulotomy].

PubMed

Spyridaki, M; Höh, H

2010-03-01

The aim of this study was to evaluate the incidence of posterior capsule opacification up to 50 months following 1.7-mm bimanual MICS-cataract surgery. Bimanual MICS cataract surgery was performed in 197 eyes (135 patients) via two 1.7-mm corneal incisions. Four MICS acrylic foldable IOLs were implanted: AcriSmart 48S-5, n = 54 (Acritec GmbH, Hennigsdorf, now AT.Smart 48S Carl-Zeiss-Meditec, AG, Jena, Germany), ThinLens UltraChoice 1.0, n = 53 (Technomed GmbH, Baesweiler, Germany), AcriFlex 46, n = 41 und AcriFlex 48 CSE, n = 7 (Acrimed GmbH, Berlin, now: Lentis L-303, Oculentis GmbH, Berlin, Germany) and CareFlex, n = 43 (w2o Medizintechnik AG, Bruchsal, Germany). Statistical analysis was performed using the Kaplan-Meier technique. High levels of completeness of follow-up rates were: ThinLens 96%, CareFlex 100%, AcriSmart 93%, AcriFlex 92%. The capsulotomy rate was 43.13% for ThinLens within a mean/max. follow-up period of 801/1131 days, 34.88% for CareFlex (565/872 days), 40% for AcriSmart (988/1506 days) and 15.91% for AcriFlex (728/975 days). By limiting the follow-up period to a comparable maximum of 850 days for all four IOLs, our capsulotomy rates were as follows: ThinLens 33.33%, CareFlex 32.56 %, AcriSmart 20.0% and AcriFlex 11.36%. MICS IOLs have higher capsulotomy rates than hydrophobic acrylic lenses and sharp-edged silicone lenses. In literature comparisons MICS-IOLs do not exceed the variance levels of capsulotomy rates of PMMA, hydrophilic acrylic and silicone lenses without sharp edges. Cases of decentration or luxation of MICS-IOLs following Neodym:YAG laser capsulotomy were not detected. Capsulotomy frequency with the CareFlex was statistically significantly higher in comparison to the AcriSmart (Log Rank Mantel Cox Test, p = 0.007) and AcriFlex (log rank Mantel Cox test, p = 0.002). Capsulotomy rates observed varied for the four MICS-IOL-types tested. The posterior capsule opacification frequency of the two best MICS-IOLs (AcriFlex, AcriSmart) did not exceed the higher variance levels of posterior capsule opacification rates of the round-edged "conventional" non-MICS IOLs of PMMA, silicone or hydrophilic acryl material. Sharp-edged silicone or hydrophobic acrylic "conventional" lenses have shown lower posterior capsule opacification rates. Georg Thieme Verlag KG Stuttgart, New York.

Fish bioconcentration studies with column-generated analyte concentrations of highly hydrophobic organic chemicals.

PubMed

Schlechtriem, Christian; Böhm, Leonard; Bebon, Rebecca; Bruckert, Hans-Jörg; Düring, Rolf-Alexander

2017-04-01

The performance of aqueous exposure bioconcentration fish tests according to Organisation for Economic Co-operation and Development (OECD) guideline 305 requires the possibility of preparing stable aqueous concentrations of the test substances. For highly hydrophobic organic chemicals (HOCs; octanol-water partition coefficient [log K OW ] > 5), testing via aqueous exposure may become increasingly difficult. A solid-phase desorption dosing system was developed to generate stable concentrations of HOCs without using solubilizing agents. The system was tested with hexachlorobenzene (HCB), o-terphenyl (oTP), polychlorinated biphenyl (PCB) 153, and dibenz[a,h]anthracene (DBA) (log K OW 5.5-7.8) in 2 flow-through fish tests with rainbow trout (Oncorhynchus mykiss). The analysis of the test media applied during the bioconcentration factor (BCF) studies showed that stable analyte concentrations of the 4 HOCs were maintained in the test system over an uptake period of 8 wk. Bioconcentration factors (L kg -1 wet wt) were estimated for HCB (BCF 35 589), oTP (BCF 12 040), and PCB 153 (BCF 18 539) based on total water concentrations. No bioconcentration could be determined for DBA, probably because of the rapid metabolism of the test item. The solid-phase desorption dosing system is suitable to provide stable aqueous concentrations of HOCs required to determine the bioconcentration in fish and represents a viable alternative to the use of solubilizing agents for the preparation of test solutions. Environ Toxicol Chem 2017;36:906-916. © 2016 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC. © 2016 The Authors. Environmental Toxicology and Chemistry Published by Wiley Periodicals, Inc. on behalf of SETAC.

Coastal California's Fog Aerobiology and Ecology: Designing and Testing an Optimal Passive Impactor Collection Unit

NASA Astrophysics Data System (ADS)

Gentry, D.; Whinnery, J. T.; Ly, V. T.; Travers, S. V.; Sagaga, J.; Dahlgren, R. P.

2017-12-01

Microorganisms play a major role in our biosphere due to their ability to alter water, carbon and other geochemical cycles. Fog and low-level cloud water can play a major role in dispersing and supporting such microbial diversity. An ideal region to gather these microorganisms for characterization is the central coast of California, where dense fog is common. Fog captured from an unmanned aerial vehicle (UAV) at different altitudes will be analyzed to better understand the nature of microorganisms in the lower atmosphere and their potential geochemical impacts. The capture design consists of a square-meter hydrophobic mesh that hangs from a carbon fiber rod attached to a UAV. The DJI M600, a hexacopter, will be utilized as the transport for the payload, the passive impactor collection unit (PICU). The M600 will hover in a fog bank at altitudes between 10 and 100 m collecting water samples via the PICU. A computational flow dynamics (CFD) model will optimize the PICU's size, shape and placement for maximum capture efficiency and to avoid contamination from the UAV downwash. On board, there will also be an altitude, temperature and barometric pressure sensor whose output is logged to an SD card. A scale model of the PICU has been tested with several different types of hydrophobic meshes in a fog chamber at 90-95% humidity; polypropylene was found to capture the fog droplets most efficiently at a rate of .0042 g/cm2/hour. If the amount collected is proportional to the area of mesh, the estimated amount of water collected under optimal fog and flight conditions by the impactor is 21.3 g. If successful, this work will help identify the organisms living in the lower atmosphere as well as their potential geochemical impacts.

Application of passive sampling for measuring dissolved concentrations of organic contaminants in the water column at three marine superfund sites.

PubMed

Burgess, Robert M; Lohmann, Rainer; Schubauer-Berigan, Joseph P; Reitsma, Pamela; Perron, Monique M; Lefkovitz, Lisa; Cantwell, Mark G

2015-08-01

Currently, there is an effort under way to encourage remedial project managers at contaminated sites to use passive sampling to collect freely dissolved concentrations (Cfree ) of hydrophobic organic contaminants to improve site assessments. The objective of the present study was to evaluate the use of passive sampling for measuring water column Cfree for several hydrophobic organic contaminants at 3 US Environmental Protection Agency Superfund sites. Sites investigated included New Bedford Harbor (New Bedford, MA, USA), Palos Verdes Shelf (Los Angeles, CA, USA), and Naval Station Newport (Newport, RI, USA); and the passive samplers evaluated were polyethylene, polydimethylsiloxane-coated solid-phase microextraction fibers, semipermeable membrane devices, and polyoxymethylene. In general, the different passive samplers demonstrated good agreement, with Cfree values varying by a factor of 2 to 3. Further, at New Bedford Harbor, where conventional water sample concentrations were also measured (i.e., grab samples), passive sampler-based Cfree values agreed within a factor of 2. These findings suggest that all of the samplers were experiencing and measuring similar Cfree during their respective deployments. Also, at New Bedford Harbor, a strong log-linear, correlative, and predictive relationship was found between polyethylene passive sampler accumulation and lipid-normalized blue mussel bioaccumulation of polychlorinated biphenyls (r(2)  = 0.92, p < 0.05). The present study demonstrates the utility of passive sampling for generating scientifically accurate water column Cfree values, which is critical for making informed environmental management decisions at contaminated sediment sites. Published 2015 SETAC. This article is a US Government work and is in the public domain in the USA.

The effect of surface characteristics on the transport of multiple Escherichia coli isolates in large scale columns of quartz sand.

PubMed

Lutterodt, G; Basnet, M; Foppen, J W A; Uhlenbrook, S

2009-02-01

Bacteria properties play an important role in the transport of bacteria in groundwater, but their role, especially for longer transport distances (>0.5 m) has not been studied. Thereto, we studied the effects of cell surface hydrophobicity, outer surface potential (OSP), cell sphericity, motility, and Ag43 protein expression on the outer cell surface for a number of E. coli strains, obtained from the environment on their transport behavior in columns of saturated quartz sand of 5 m height in two solutions: demineralized (DI) water and artificial groundwater (AGW). In DI water, sticking efficiencies ranged between 0.1 and 0.4 at the column inlet, and then decreased with transport distance to 0.02-0.2. In AGW, sticking efficiencies were on average 1log-unit higher than those in DI (water). Bacteria motility and Ag43 expression affected attachment with a (high) statistical significance. In contrast, hydrophobicity, OSP and cell sphericity did not significantly correlate with sticking efficiency. However, for transport distances more than 0.33 m, the correlation between sticking efficiency, Ag43 expression, and motility became insignificant. We concluded that Ag43 and motility played an important role in E. coli attachment to quartz grain surfaces, and that the transport distance dependent sticking efficiency reductions were caused by motility and Ag43 expression variations within a population. The implication of our findings is that less motile bacteria with little or no Ag43 expression may travel longer distances once they enter groundwater environments. In future studies, the possible effect of bacteria surface structures, like fimbriae, pili and surface proteins on bacteria attachment need to be considered more systematically in order to arrive at more meaningful inter-population comparisons of the transport behavior of E. coli strains in aquifers.

Incorporation of hydrophobized mineral particles in activated sludge flocs: a way to assess ballasting efficiency.

PubMed

Defontaine, G; Thormann, J; Lartiges, B S; El Samrani, A G; Barrs, O

2005-01-01

The role of mineral surface hydrophobicity in attachment to activated sludge flocs was investigated. Fluorite and quartz particles of similar granulometry were hydrophobized by adsorbing sodium oleate and dodecylamine chloride, respectively. Mineral hydrophobicity was assessed by flotation expriments. The attachment of particles to microbial flocs was determined by optical microscopy. The results indicate that hydrophobized particles are always better incorporated within activated sludge flocs than non-coated particles. A comparison with Aquatal particles used as sludge ballast reveals that hydrophobized minerals are associated with microbial flocs to the same extent.

Hydrophobic-Core Microcapsules and Their Formation

NASA Technical Reports Server (NTRS)

Buhrow, Jerry W. (Inventor); Li, Wenyan (Inventor); Jolley, Scott T. (Inventor); Calle, Luz M. (Inventor)

2016-01-01

Hydrophobic-core microcapsules and methods of their formation are provided. A hydrophobic-core microcapsule may include a shell that encapsulates a hydrophobic substance with a core substance, such as dye, corrosion indicator, corrosion inhibitor, and/or healing agent, dissolved or dispersed therein. The hydrophobic-core microcapsules may be formed from an emulsion having hydrophobic-phase droplets, e.g., containing the core substance and shell-forming compound, dispersed in a hydrophilic phase. The shells of the microcapsules may be capable of being broken down in response to being contacted by an alkali, e.g., produced during corrosion, contacting the shell.

Synthesis of biocompatible hydrophobic silica-gelatin nano-hybrid by sol-gel process.

PubMed

Smitha, S; Shajesh, P; Mukundan, P; Nair, T D R; Warrier, K G K

2007-03-15

Silica-biopolymer hybrid has been synthesised using colloidal silica as the precursor for silica and gelatin as the biopolymer counterpart. The surface modification of the hybrid material has been done with methyltrimethoxysilane leading to the formation of biocompatible hydrophobic silica-gelatin hybrid. Here we are reporting hydrophobic silica-gelatin hybrid and coating precursor for the first time. The hybrid gel has been evaluated for chemical modification, thermal degradation, hydrophobicity, particle size, transparency under the UV-visible region and morphology. FTIR spectroscopy has been used to verify the presence of CH(3) groups which introduce hydrophobicity to the SiO2-MTMS-gelatin hybrids. The hydrophobic property has also been tailored by varying the concentration of methyltrimethoxysilane. Contact angle by Wilhelmy plate method of transparent hydrophobic silica-gelatin coatings has been found to be as high as approximately 95 degrees . Oxidation of the organic group which induces the hydrophobic character occurs at 530 degrees C which indicates that the surface hydrophobicity is retained up to that temperature. Optical transmittance of SiO2-MTMS-gelatin hybrid coatings on glass substrates has been found to be close to 100% which will enable the hybrid for possible optical applications and also for preparation of transparent biocompatible hydrophobic coatings on biological substrates such as leather.

Broad spectrum antimicrobial activity of melimine covalently bound to contact lenses.

PubMed

Dutta, Debarun; Cole, Nerida; Kumar, Naresh; Willcox, Mark D P

2013-01-07

To develop a stable antimicrobial contact lens, which is effective against the International Organization for Standardization (ISO) panel microorganisms, Acanthamoeba castellanii and drug resistant strains of Pseudomonas aeruginosa and Staphylococcus aureus. Melimine was covalently incorporated into etafilcon A lenses. The amount of peptide present on the lens surface was quantified using amino acid analysis. After coating, the heat stability (121°C), lens surface hydrophobicity (by captive bubble), and in vitro cytotoxicity to mouse L929 cells of the lenses were investigated. Antimicrobial activity against the micro-organisms was evaluated by viable plate count and fluorescence microscopy, measuring the proportion of cell death compared with control lenses with no melimine. The most effective concentration was determined to be 152 ± 44 μg lens(-1) melimine on the lens surface. After coating, lenses were relatively hydrophilic and were nontoxic to mammalian cells. The activity remained high after autoclaving (e.g., 3.1, 3.9, 1.2, and 1.0 log inhibition against P. aeruginosa, S. aureus, A. castellanii, and Fusarium solani, respectively). Fluorescence microscopy confirmed significantly reduced (P < 0.001) adhesion of viable bacteria to melimine contact lenses. Viable count confirmed that lenses were active against all the bacteria and fungi from the ISO panel, Acanthamoeba and gave at least 2 log inhibition against all the multidrug resistant S. aureus and P. aeruginosa strains. Melimine may offer excellent potential for development as a broad spectrum antimicrobial coating for contact lenses, showing activity against all the bacterial and fungal ISO panel microorganisms, Acanthamoeba, and antibiotic resistant strains of P. aeruginosa and S. aureus.

Adsorption of hydrophobin on different self-assembled monolayers: the role of the hydrophobic dipole and the electric dipole.

PubMed

Peng, Chunwang; Liu, Jie; Zhao, Daohui; Zhou, Jian

2014-09-30

In this work, the adsorptions of hydrophobin (HFBI) on four different self-assembled monolayers (SAMs) (i.e., CH3-SAM, OH-SAM, COOH-SAM, and NH2-SAM) were investigated by parallel tempering Monte Carlo and molecular dynamics simulations. Simulation results indicate that the orientation of HFBI adsorbed on neutral surfaces is dominated by a hydrophobic dipole. HFBI adsorbs on the hydrophobic CH3-SAM through its hydrophobic patch and adopts a nearly vertical hydrophobic dipole relative to the surface, while it is nearly horizontal when adsorbed on the hydrophilic OH-SAM. For charged SAM surfaces, HFBI adopts a nearly vertical electric dipole relative to the surface. HFBI has the narrowest orientation distribution on the CH3-SAM, and thus can form an ordered monolayer and reverse the wettability of the surface. For HFBI adsorption on charged SAMs, the adsorption strength weakens as the surface charge density increases. Compared with those on other SAMs, a larger area of the hydrophobic patch is exposed to the solution when HFBI adsorbs on the NH2-SAM. This leads to an increase of the hydrophobicity of the surface, which is consistent with the experimental results. The binding of HFBI to the CH3-SAM is mainly through hydrophobic interactions, while it is mediated through a hydration water layer near the surface for the OH-SAM. For the charged SAM surfaces, the adsorption is mainly induced by electrostatic interactions between the charged surfaces and the oppositely charged residues. The effect of a hydrophobic dipole on protein adsorption onto hydrophobic surfaces is similar to that of an electric dipole for charged surfaces. Therefore, the hydrophobic dipole may be applied to predict the probable orientations of protein adsorbed on hydrophobic surfaces.

Hydrophobic folding units derived from dissimilar monomer structures and their interactions.

PubMed

Tsai, C J; Nussinov, R

1997-01-01

We have designed an automated procedure to cut a protein into compact hydrophobic folding units. The hydrophobic units are large enough to contain tertiary non-local interactions, reflecting potential nucleation sites during protein folding. The quality of a hydrophobic folding unit is evaluated by four criteria. The first two correspond to visual characterization of a structural domain, namely, compactness and extent of isolation. We use the definition of Zehfus and Rose (Zehfus MH, Rose GD, 1986, Biochemistry 25:35-340) to calculate the compactness of a cut protein unit. The isolation of a unit is based on the solvent accessible surface area (ASA) originally buried in the interior and exposed to the solvent after cutting. The third quantity is the hydrophobicity, equivalent to the fraction of the buried non-polar ASA with respect to the total non-polar ASA. The last criterion in the evaluation of a folding unit is the number of segments it includes. To conform with the rationale of obtaining hydrophobic units, which may relate to early folding events, the hydrophobic interactions are implicitly and explicitly applied in their generation and assessment. We follow Holm and Sander (Holm L, Sander C, 1994, Proteins 19:256-268) to reduce the multiple cutting-point problem to a one-dimensional search for all reasonable trial cuts. However, as here we focus on the hydrophobic cores, the contact matrix used to obtain the first non-trivial eigenvector contains only hydrophobic contracts, rather than all, hydrophobic and hydrophilic, interactions. This dataset of hydrophobic folding units, derived from structurally dissimilar single chain monomers, is particularly useful for investigations of the mechanism of protein folding. For cases where there are kinetic data, the one or more hydrophobic folding units generated for a protein correlate with the two or with the three-state folding process observed. We carry out extensive amino acid sequence order independent structural comparisons to generate a structurally non-redundant set of hydrophobic folding units for fold recognition and for statistical purposes.

A preliminary evaluation of the relationship between bioconcentration and hydrophobicity for surfactants

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

Tolls, J.; Sijm, D.T.H.M.

1995-10-01

A statistical analysis was done of the relationship between hydrophobicity and bioconcentration parameters (uptake and elimination rate constants and bioconcentration factor) predicted by the diffusive mass-transfer (DMT) concept of bioconcentration developed previously. The authors employed polychlorinated biphenyls and benzenes (PCB/zs) as model compounds and the octanol/water partition coefficient as hydrophobicity parameter. They conclude that the model is consistent with the data. Subsequently, they applied the DMT concept to a set of preliminary bioconcentration data for surfactants using the critical micelle concentration (CMC) as hydrophobicity parameter. The obtained relationships qualitatively agree with the DMT concept, indicating that hydrophobicity is of greatmore » influence on surfactant bioconcentration. Finally, they investigated the hydrophobicity-bioconcentration relationships of surfactants and PCB/zs using aqueous solubility as common hydrophobicity parameter and found the relationships between the bioconcentration parameters and hydrophobicity to agree with the DMT concept. These findings are based on total radiolabel data. Therefore, they need to be confirmed using compound-specific surfactant bioconcentration data.« less

Characterization and comparison of hydrophobic neutral and hydrophobic acid dissolved organic carbon isolated from three municipal landfill leachates

USGS Publications Warehouse

Nanny, Mark A.; Ratasuk, Nopawan

2002-01-01

The acid-precipitated (AP) and acid-soluble (AS) fractions of the combined hydrophobic neutral and hydrophobic acid dissolved organic carbon (DOC) were isolated from leachate collected from three municipal landfills of different age and redox conditions. The AP and the AS combined hydrophobic neutral and hydrophobic acid DOC comprised 6–15% and 51–66%, respectively, of the leachate nonpurgable organic carbon. Elemental analysis, infra-red spectroscopy, 13C CP-MAS nuclear magnetic resonance spectroscopy and dipolar dephasing experiments, and thermochemolysis gas chromatography/mass spectrometry results showed that the AP and AS fractions of hydrophobic neutral and hydrophobic acid DOC are highly aliphatic, with linear and branching moieties, and less oxidized than most terrestrial and aquatic humic substances. Very little, if any, polysaccharide or cellulose, lignin, or cutin components comprise these fractions. It is hypothesized that a majority of the organic carbon in these fractions originates highly branched, cyclic aliphatic organic compounds.

A generalized analysis of hydrophobic and loop clusters within globular protein sequences

PubMed Central

Eudes, Richard; Le Tuan, Khanh; Delettré, Jean; Mornon, Jean-Paul; Callebaut, Isabelle

2007-01-01

Background Hydrophobic Cluster Analysis (HCA) is an efficient way to compare highly divergent sequences through the implicit secondary structure information directly derived from hydrophobic clusters. However, its efficiency and application are currently limited by the need of user expertise. In order to help the analysis of HCA plots, we report here the structural preferences of hydrophobic cluster species, which are frequently encountered in globular domains of proteins. These species are characterized only by their hydrophobic/non-hydrophobic dichotomy. This analysis has been extended to loop-forming clusters, using an appropriate loop alphabet. Results The structural behavior of hydrophobic cluster species, which are typical of protein globular domains, was investigated within banks of experimental structures, considered at different levels of sequence redundancy. The 294 more frequent hydrophobic cluster species were analyzed with regard to their association with the different secondary structures (frequencies of association with secondary structures and secondary structure propensities). Hydrophobic cluster species are predominantly associated with regular secondary structures, and a large part (60 %) reveals preferences for α-helices or β-strands. Moreover, the analysis of the hydrophobic cluster amino acid composition generally allows for finer prediction of the regular secondary structure associated with the considered cluster within a cluster species. We also investigated the behavior of loop forming clusters, using a "PGDNS" alphabet. These loop clusters do not overlap with hydrophobic clusters and are highly associated with coils. Finally, the structural information contained in the hydrophobic structural words, as deduced from experimental structures, was compared to the PSI-PRED predictions, revealing that β-strands and especially α-helices are generally over-predicted within the limits of typical β and α hydrophobic clusters. Conclusion The dictionary of hydrophobic clusters described here can help the HCA user to interpret and compare the HCA plots of globular protein sequences, as well as provides an original fundamental insight into the structural bricks of protein folds. Moreover, the novel loop cluster analysis brings additional information for secondary structure prediction on the whole sequence through a generalized cluster analysis (GCA), and not only on regular secondary structures. Such information lays the foundations for developing a new and original tool for secondary structure prediction. PMID:17210072

Surface characterization and adhesion and friction properties of hydrophobic leaf surfaces.

PubMed

Burton, Zachary; Bhushan, Bharat

2006-01-01

Super-hydrophobic surfaces as well as low adhesion and friction are desirable for various industrial applications. Certain plant leaves are known to be hydrophobic in nature. These leaves are hydrophobic due to the presence of microbumps and a thin wax film on the surface of the leaf. The purpose of this study is to fully characterize the leaf surface and to separate out the effects of the microbumps and the wax on the hydrophobicity. Furthermore, the adhesion and friction properties of the leaves, with and without wax, are studied. Using an optical profiler and an atomic/friction force microscope (AFM/FFM), measurements on the hydrophobic leaves, both with and without wax, were made to fully characterize the leaf surface. Using a model that predicts contact angle as a function of roughness, the roughness factor for the hydrophobic leaves has been calculated, which is used to calculate the contact angle for a flat leaf surface. It is shown that both the microbumps and the wax play an equally important role in the hydrophobic nature as well as adhesion and friction of the leaf. This study will be useful in developing super-hydrophobic surfaces.

Features of the corrosion protection of aluminium alloys by creation of hydrophobic coatings

NASA Astrophysics Data System (ADS)

Sinebryukhov, S. L.; Gnedenkov, S. V.; Egorkin, V. S.; Vyaliy, I. E.

2017-09-01

Results of the study of hydrophobic layers on aluminum alloy, which underwent plasma electrolytic oxidation (PEO) and subsequent deposition of the hydrophobic agent have been described. Coatings formed by deposition of dispersion of the hydrophobic agent containing SiO2 nanoparticles on the surface of the PEO-layer are characterized by high contact angles and inhibitive properties. The formed composite layers were found to be characterized with hydrophobicity and high barrier properties.

Statistical Analyses of Hydrophobic Interactions: A Mini-Review

DOE PAGES

Pratt, Lawrence R.; Chaudhari, Mangesh I.; Rempe, Susan B.

2016-07-14

Here this review focuses on the striking recent progress in solving for hydrophobic interactions between small inert molecules. We discuss several new understandings. First, the inverse temperature phenomenology of hydrophobic interactions, i.e., strengthening of hydrophobic bonds with increasing temperature, is decisively exhibited by hydrophobic interactions between atomic-scale hard sphere solutes in water. Second, inclusion of attractive interactions associated with atomic-size hydrophobic reference cases leads to substantial, nontrivial corrections to reference results for purely repulsive solutes. Hydrophobic bonds are weakened by adding solute dispersion forces to treatment of reference cases. The classic statistical mechanical theory for those corrections is not accuratemore » in this application, but molecular quasi-chemical theory shows promise. Lastly, because of the masking roles of excluded volume and attractive interactions, comparisons that do not discriminate the different possibilities face an interpretive danger.« less

A simple atomic-level hydrophobicity scale reveals protein interfacial structure.

PubMed

Kapcha, Lauren H; Rossky, Peter J

2014-01-23

Many amino acid residue hydrophobicity scales have been created in an effort to better understand and rapidly characterize water-protein interactions based only on protein structure and sequence. There is surprisingly low consistency in the ranking of residue hydrophobicity between scales, and their ability to provide insightful characterization varies substantially across subject proteins. All current scales characterize hydrophobicity based on entire amino acid residue units. We introduce a simple binary but atomic-level hydrophobicity scale that allows for the classification of polar and non-polar moieties within single residues, including backbone atoms. This simple scale is first shown to capture the anticipated hydrophobic character for those whole residues that align in classification among most scales. Examination of a set of protein binding interfaces establishes good agreement between residue-based and atomic-level descriptions of hydrophobicity for five residues, while the remaining residues produce discrepancies. We then show that the atomistic scale properly classifies the hydrophobicity of functionally important regions where residue-based scales fail. To illustrate the utility of the new approach, we show that the atomic-level scale rationalizes the hydration of two hydrophobic pockets and the presence of a void in a third pocket within a single protein and that it appropriately classifies all of the functionally important hydrophilic sites within two otherwise hydrophobic pores. We suggest that an atomic level of detail is, in general, necessary for the reliable depiction of hydrophobicity for all protein surfaces. The present formulation can be implemented simply in a manner no more complex than current residue-based approaches. © 2013.

Effect of water velocity on the uptake of polychlorinated biphenyls (PCBs) by silicone rubber (SR) and low-density polyethylene (LDPE) passive samplers: an assessment of the efficiency of performance reference compounds (PRCs) in river-like flow conditions.

PubMed

Estoppey, Nicolas; Schopfer, Adrien; Omlin, Julien; Esseiva, Pierre; Vermeirssen, Etiënne L M; Delémont, Olivier; De Alencastro, Luiz F

2014-11-15

One aim of this study is to determine the impact of water velocity on the uptake of indicator polychlorinated biphenyls (iPCBs) by silicone rubber (SR) and low-density polyethylene (LDPE) passive samplers. A second aim is to assess the efficiency of performance reference compounds (PRCs) to correct for the impact of water velocity. SR and LDPE samplers were spiked with 11 or 12 PRCs and exposed for 6 weeks to four different velocities (in the range of 1.6 to 37.7 cm s(-1)) in river-like flow conditions using a channel system supplied with river water. A relationship between velocity and the uptake was found for each iPCB and enables to determine expected changes in the uptake due to velocity variations. For both samplers, velocity increases from 2 to 10 cm s(-1), 30 cm s(-1) (interpolated data) and 100 cm s(-1) (extrapolated data) lead to increases of the uptake which do not exceed a factor of 2, 3 and 4.5, respectively. Results also showed that the influence of velocity decreased with increasing the octanol-water coefficient partition (log K(ow)) of iPCBs when SR is used whereas the opposite effect was observed for LDPE. Time-weighted average (TWA) concentrations of iPCBs in water were calculated from iPCB uptake and PRC release. These calculations were performed using either a single PRC or all the PRCs. The efficiency of PRCs to correct the impact of velocity was assessed by comparing the TWA concentrations obtained at the four tested velocities. For SR, a good agreement was found among the four TWA concentrations with both methods (average RSD<10%). Also for LDPE, PRCs offered a good correction of the impact of water velocity (average RSD of about 10 to 20%). These results contribute to the process of acceptance of passive sampling in routine regulatory monitoring programs. Copyright © 2014 Elsevier B.V. All rights reserved.

Temporal trends (1987-2002) of persistent, bioaccumulative and toxic (PBT) chemicals in beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary, Canada.

PubMed

Lebeuf, Michel; Noël, Michelle; Trottier, Steve; Measures, Lena

2007-09-20

Temporal trends of persistent, bioaccumulative and toxic (PBT) chemicals were examined in beluga whales (Delphinapterus leucas) from the St. Lawrence Estuary (SLE), Canada. Blubber samples of 86 adult belugas were collected from animals stranded on the shore of the SLE between 1987 and 2002 and analyzed for several regulated PBTs, including polychlorinated biphenyls (PCBs), p,p'dichlorodiphenyltrichloroethane (DDT) and its metabolites, chlordane (CHL) and related compounds, hexachlorocyclohexane (HCH) isomers, hexachlorobenzene (HCB) and Mirex. In addition, time trends of tris(4-chlorophenyl)methane (TCPMe) and tris(4-chlorophenyl)methanol (TCPMOH), two compounds that may origin from DDT formulations, were also examined. Concentrations of most of the PBTs examined had exponentially decreased by at least a factor of two (half-life time (t(1/2))<15 years) in beluga between 1987 and 2002 while no increasing trends were observed for any of the PBTs measured. The decreasing trends of PBT concentrations in SLE beluga may be due to a decline in contamination of its diet following North American and international regulations on the use and production of these compounds or by a change in its diet itself or by a combination of both. Some PBTs did not exhibit any significant trends in beluga possibly because the most intense elimination phase subsequent to legislative regulations occurred prior to the 1987-2002 time period. Other chemicals, such gamma-HCH, did not significantly decrease likely because they are still currently used in some restricted applications. Conversely, alpha-HCH showed a significant decreasing trend indicating that SigmaHCHs is not representative of all HCHs. Both TCPMe and TCPMOH exhibited no trends in beluga during the time period examined. The metabolic capacity of SLE beluga has apparently accelerated the depletion of at least one PBT, namely CB-28/31. A significant relationship between the half-life of PBTs in beluga and log Kow was observed for most of the chemicals examined. Several factors are expected to have influenced the temporal changes of PBT concentrations in beluga which limit the usefulness of this species as a bioindicator of changes in PBT contamination in the SLE ecosystem.

Improved predictive model for n-decane kinetics across species, as a component of hydrocarbon mixtures.

PubMed

Merrill, E A; Gearhart, J M; Sterner, T R; Robinson, P J

2008-07-01

n-Decane is considered a major component of various fuels and industrial solvents. These hydrocarbon products are complex mixtures of hundreds of components, including straight-chain alkanes, branched chain alkanes, cycloalkanes, diaromatics, and naphthalenes. Human exposures to the jet fuel, JP-8, or to industrial solvents in vapor, aerosol, and liquid forms all have the potential to produce health effects, including immune suppression and/or neurological deficits. A physiologically based pharmacokinetic (PBPK) model has previously been developed for n-decane, in which partition coefficients (PC), fitted to 4-h exposure kinetic data, were used in preference to measured values. The greatest discrepancy between fitted and measured values was for fat, where PC values were changed from 250-328 (measured) to 25 (fitted). Such a large change in a critical parameter, without any physiological basis, greatly impedes the model's extrapolative abilities, as well as its applicability for assessing the interactions of n-decane or similar alkanes with other compounds in a mixture model. Due to these limitations, the model was revised. Our approach emphasized the use of experimentally determined PCs because many tissues had not approached steady-state concentrations by the end of the 4-h exposures. Diffusion limitation was used to describe n-decane kinetics for the brain, perirenal fat, skin, and liver. Flow limitation was used to describe the remaining rapidly and slowly perfused tissues. As expected from the high lipophilicity of this semivolatile compound (log K(ow) = 5.25), sensitivity analyses showed that parameters describing fat uptake were next to blood:air partitioning and pulmonary ventilation as critical in determining overall systemic circulation and uptake in other tissues. In our revised model, partitioning into fat took multiple days to reach steady state, which differed considerably from the previous model that assumed steady-state conditions in fat at 4 h post dosing with 1200 ppm. Due to these improvements, and particularly the reconciliation between measured and fitted partition coefficients, especially fat, we have greater confidence in using the proposed model for dose, species, and route of exposure extrapolations and as a harmonized model approach for other hydrocarbon components of mixtures.

Dynamics of Wetting of Ultra Hydrophobic Surfaces

NASA Astrophysics Data System (ADS)

Mohammad Karim, Alireza; Kim, Jeong-Hyun; Rothstein, Jonathan; Kavehpour, Pirouz; Mechanical and Industrial Engineering, University of Massachusetts, Amherst Collaboration

2013-11-01

Controlling the surface wettability of hydrophobic and super hydrophobic surfaces has extensive industrial applications ranging from coating, painting and printing technology and waterproof clothing to efficiency increase in power and water plants. This requires enhancing the knowledge about the dynamics of wetting on these hydrophobic surfaces. We have done experimental investigation on the dynamics of wetting on hydrophobic surfaces by looking deeply in to the dependency of the dynamic contact angles both advancing and receding on the velocity of the three-phase boundary (Solid/Liquid/Gas interface) using the Wilhelmy plate method with different ultra-hydrophobic surfaces. Several fluids with different surface tension and viscosity are used to study the effect of physical properties of liquids on the governing laws.

Characterisation of nanomaterial hydrophobicity using engineered surfaces

NASA Astrophysics Data System (ADS)

Desmet, Cloé; Valsesia, Andrea; Oddo, Arianna; Ceccone, Giacomo; Spampinato, Valentina; Rossi, François; Colpo, Pascal

2017-03-01

Characterisation of engineered nanomaterials (NMs) is of outmost importance for the assessment of the potential risks arising from their extensive use. NMs display indeed a large variety of physico-chemical properties that drastically affect their interaction with biological systems. Among them, hydrophobicity is an important property that is nevertheless only slightly covered by the current physico-chemical characterisation techniques. In this work, we developed a method for the direct characterisation of NM hydrophobicity. The determination of the nanomaterial hydrophobic character is carried out by the direct measurement of the affinity of the NMs for different collectors. Each collector is an engineered surface designed in order to present specific surface charge and hydrophobicity degrees. Being thus characterised by a combination of surface energy components, the collectors enable the NM immobilisation with surface coverage in relation to their hydrophobicity. The experimental results are explained by using the extended DLVO theory, which takes into account the hydrophobic forces acting between NMs and collectors.

Hydrophobic interactions between dissimilar surfaces

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

Yoon, R.H.; Flinn, D.H.; Rabinovich, Y.I.

1997-01-15

An atomic force microscope (AFM) was used to measure surface forces between a glass sphere and a silica plate. When the measurements were conducted between untreated surfaces, a short-range hydration force with decay lengths of 0.4 and 3.0 nm was observed. When the surfaces were hydrophobized with octadecyltrichlorosilane (OTS), on the other hand, long-range hydrophobic forces with decay lengths in the range of 2--32 nm were observed. The force measurements were conducted between surfaces having similar and dissimilar hydrophobicities so that the results may be used for deriving an empirical combining rule. It was found that the power law forcemore » constants for asymmetric interactions are close to the geometric means of those for symmetric interactions. Thus, hydrophobic force constants can be combined in the same manner as the Hamaker constants. A plot of the power law force constants versus water contact angles suggests that the hydrophobic force is uniquely determined by contact angle. These results will be useful in predicting hydrophobic forces for asymmetric interactions and in estimating hydrophobic forces from contact angles.« less

Fabrication of TiO2/EP super-hydrophobic thin film on filter paper surface.

PubMed

Gao, Zhengxin; Zhai, Xianglin; Liu, Feng; Zhang, Ming; Zang, Deli; Wang, Chengyu

2015-09-05

A composite filter paper with super-hydrophobicity was obtained by adhering micro/nano structure of amorphous titanium dioxide on the filter paper surface with modifying low surface energy material. By virtue of the coupling agent, which plays an important part in bonding amorphous titanium dioxide and epoxy resin, the structure of super-hydrophobic thin film on the filter paper surface is extremely stable. The microstructure of super-hydrophobic filter paper was characterized by scanning electron microscopy (SEM), the images showed that the as-prepared filter paper was covered with uniform amorphous titanium dioxide particles, generating a roughness structure on the filter paper surface. The super-hydrophobic performance of the filter paper was characterized by water contact angle measurements. The observations showed that the wettability of filter paper samples transformed from super-hydrophilicity to super-hydrophobicity with the water contact angle of 153 ± 1°. Some experiments were also designed to test the effect of water-oil separation and UV-resistant by the super-hydrophobic filter paper. The prepared super-hydrophobic filter paper worked efficiently and simply in water-oil separation as well as enduringly in anti-UV property after the experiments. This method offers an opportunity to the practical applications of the super-hydrophobic filter paper. Copyright © 2015 Elsevier Ltd. All rights reserved.

Manipulating Hydrophobic Interactions in Associative Polymer Solutions via Surfactant-Cyclodextrin Complexation

NASA Astrophysics Data System (ADS)

Talwar, Sachin; Harding, Jonathon; Khan, Saad A.

2008-07-01

Associative polymers in combination with cyclodextrin (CD) provide a potent tool to manipulate the solution rheology of aqueous solutions. In this study, we discuss the viability and scope of employing surfactants in such systems to facilitate a more versatile and effective tailoring of rheological properties. A model hydrophobically modified alkali-soluble emulsion (HASE) polymer is used which forms a transient physical network of intra- and inter-molecular hydrophobic junctions in solution arising from the interactions between hydrophobic groups grafted on the polymer backbone. The presence of these hydrophobic junctions significantly enhances the solution rheological properties with both the steady state viscosity and dynamic moduli exhibiting an increase by several orders of magnitude. The ability of nonionic surfactants to modulate and recover the hydrophobic interactions in these polymer solutions in the presence of cyclodextrin is examined. The presence of either a- or β-CD results in a dramatic decrease in viscosity and viscoelastic properties of the HASE polymer solution resulting from the encapsulation of polymer hydrophobes by CDs. Addition of nonionic surfactants to such systems promotes a competition between CDs and surfactant molecules to complex with polymer hydrophobes thereby altering the hydrophobic interactions. In this regard, nonylphenol ethoxylates (NPe) with different ethylene oxide (EO) chain lengths, which determine the surfactant hydrophilic-lipophilic balance (HLB), are used.

Bioconcentration kinetics of hydrophobic chemicals in different densities of Chlorella pyrenoidosa

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

Sijm, D.T.H.M.; Broersen, K.W.; Roode, D.F. de

1998-09-01

Algal density-dependent bioconcentration factors and rate constants were determined for a series of hydrophobic compounds in Chlorella pyrenoidosa. The apparent uptake rate constants of the hydrophobic compounds in algae varied between 200 and 710,000 L/kg/d, slightly increased with hydrophobicity within an experiment, were relatively constant for each algal density, and fitted fairly within existing allometric relationships. The bioavailability of the hydrophobic test compounds was significantly reduced by sorption by algal exudates. The sorption coefficients of the hydrophobic compounds to the algal exudates were between 80 and 1,200 L/kg, and were for most algal densities in the same order of magnitudemore » as the apparent bioconcentration factors to the algae, that is, between 80 and 60,200 L/kg. In typical field situations, however, no significant reduction in bioavailability due to exudates is expected. The apparent elimination rate constants of the hydrophobic compounds were high and fairly constant for each algal density and varied between 2 and 190/d. Because the apparent elimination rate constants were higher than the growth rate constant, and were independent of hydrophobicity, the authors speculated that other factors dominate excretion, such as exudate excretion-enhanced elimination. Bioconcentration factors increased less than proportional with hydrophobicity, i.e., the octanol-water partition coefficient [K{sub ow}]. The role of algal composition in bioconcentration is evaluated. Bioconcentrations (kinetics) of hydrophobic compounds that are determined at high algal densities should be applied with caution to field situations.« less

Derivatizing weak polyelectrolytes--solution properties, self-aggregation, and association with anionic surfaces of hydrophobically modified poly(ethylene imine).

PubMed

Griffiths, Peter C; Paul, Alison; Fallis, Ian A; Wellappili, Champa; Murphy, Damien M; Jenkins, Robert; Waters, Sarah J; Nilmini, Renuka; Heenan, Richard K; King, Stephen M

2007-10-15

The physical properties of weak polyelectrolytes may be tailored via hydrophobic modification to exhibit useful properties under appropriate pH and ionic strength conditions as a consequence of the often inherently competing effects of electrostatics and hydrophobicity. Pulsed-gradient spin-echo NMR (PGSE-NMR), electron paramagnetic resonance (EPR), small-angle neutron scattering (SANS) surface tension, fluorescence, and pH titration have been used to examine the solution conformation and aggregation behavior of a series of hydrophobically modified hyperbranched poly(ethylene imine) (PEI) polymers in aqueous solution, and their interaction with sodium dodecylsulfate (SDS). PGSE-NMR gave a particularly insightful picture of the apparent molecular weight distribution. The presence of the hydrophobes led to a lower effective charge on the polymer at any given pH, compared to the (parent) nonmodified samples. Analysis of the SANS data showed that the propensity to form highly elliptical or rod-like aggregates at higher pHs, reflecting both the changes in protonation behavior induced by the hydrophobic modification and an hydrophobic interaction, but that these structures were disrupted with decreasing pH (increasing charge). The parent samples were not surface active yet the hydrophobically modified samples show pronounced surface activity and the presence of small hydrophobic domains. The surface activity increased with an increase in the degree of modification. On addition of SDS, the onset of the formation of polymer/surfactant complexes was insensitive to the degree of modification with the resultant PEI/SDS complexes resembling the size and shape of simple SDS micelles. Indeed, the presence of the SDS effectively nullifies the effects of the hydrophobe. Hydrophobic modification is therefore a viable option to tailor pH dependent properties, whose effects may be removed by the presence of surfactant.

Inhibitory effect of super-hydrophobicity on silver release and antibacterial properties of super-hydrophobic Ag/TiO2 nanotubes.

PubMed

Zhang, Licheng; Zhang, Lihai; Yang, Yun; Zhang, Wei; Lv, Houchen; Yang, Fei; Lin, Changjian; Tang, Peifu

2016-07-01

The antibacterial properties of super-hydrophobic silver (Ag) on implant surface have not yet to be fully illuminated. In our study, we investigate the protective effects of super-hydrophobic coating of silver/titanium dioxide (Ag/TiO2 ) nanotubes against bacterial pathogens, as well as its pattern of Ag release. Ag/TiO2 nanotubes are prepared by a combination of electrochemical anodization and pulse electrodeposition. The super-hydrophobic coating is prepared by modifying the surface of Ag/TiO2 nanotubes with 1H, 1H, 2H, 2H-perfluorooctyl-triethoxysilane (PTES). Surface features and Ag release are examined by SEM, X-ray photoelectron spectroscopy, contact-angle measurement, and inductively coupled plasma-mass spectrometry (ICP-MS). The antibacterial activity of super-hydrophobic coating Ag/TiO2 nanotubes is investigated both in vitro and in vivo. Consequently, the super-hydrophobic coating on Ag/TiO2 nanotubes shows a regularly arranged structure; and nano-Ag particles (10-30 nm) are evenly distributed on the surface or inside the nanotubes. The contact angles of water on the super-hydrophobic coating Ag/TiO2 nanotubes are all above 150°. In addition, the super-hydrophobic character displays a certain conserved effect that contributes to the sustained release of Ag. The super-hydrophobic Ag/TiO2 nanotubes are also effective in inhibiting bacterial adhesion, killing the adhering bacteria and preventing postoperative infection in rabbits. Therefore, it is expected that the super-hydrophobic Ag/TiO2 nanotubes which can contain the release of Ag, leading to stable release, may show a consistent surface antibacterial capability. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 104B: 1004-1012, 2016. © 2015 Wiley Periodicals, Inc.

Mapping Hydrophobicity on the Protein Molecular Surface at Atom-Level Resolution

PubMed Central

Nicolau Jr., Dan V.; Paszek, Ewa; Fulga, Florin; Nicolau, Dan V.

2014-01-01

A precise representation of the spatial distribution of hydrophobicity, hydrophilicity and charges on the molecular surface of proteins is critical for the understanding of the interaction with small molecules and larger systems. The representation of hydrophobicity is rarely done at atom-level, as this property is generally assigned to residues. A new methodology for the derivation of atomic hydrophobicity from any amino acid-based hydrophobicity scale was used to derive 8 sets of atomic hydrophobicities, one of which was used to generate the molecular surfaces for 35 proteins with convex structures, 5 of which, i.e., lysozyme, ribonuclease, hemoglobin, albumin and IgG, have been analyzed in more detail. Sets of the molecular surfaces of the model proteins have been constructed using spherical probes with increasingly large radii, from 1.4 to 20 Å, followed by the quantification of (i) the surface hydrophobicity; (ii) their respective molecular surface areas, i.e., total, hydrophilic and hydrophobic area; and (iii) their relative densities, i.e., divided by the total molecular area; or specific densities, i.e., divided by property-specific area. Compared with the amino acid-based formalism, the atom-level description reveals molecular surfaces which (i) present an approximately two times more hydrophilic areas; with (ii) less extended, but between 2 to 5 times more intense hydrophilic patches; and (iii) 3 to 20 times more extended hydrophobic areas. The hydrophobic areas are also approximately 2 times more hydrophobicity-intense. This, more pronounced “leopard skin”-like, design of the protein molecular surface has been confirmed by comparing the results for a restricted set of homologous proteins, i.e., hemoglobins diverging by only one residue (Trp37). These results suggest that the representation of hydrophobicity on the protein molecular surfaces at atom-level resolution, coupled with the probing of the molecular surface at different geometric resolutions, can capture processes that are otherwise obscured to the amino acid-based formalism. PMID:25462574

The effect of heterogeneity and surface roughness on soil hydrophobicity

NASA Astrophysics Data System (ADS)

Hallin, I.; Bryant, R.; Doerr, S. H.; Douglas, P.

2010-05-01

Soil water repellency, or hydrophobicity, can develop under both natural and anthropogenic conditions. Forest fires, vegetation decomposition, microbial activity and oil spills can all promote hydrophobic behaviour in surrounding soils. Hydrophobicity can stabilize soil organic matter pools and decrease evapotranspiration, but there are many negative impacts of hydrophobicity as well: increased erosion of topsoil, an increasingly scarce resource; increased runoff, which can lead to flooding; and decreased infiltration, which directly affects plant health. The degree of hydrophobicity expressed by soil can vary greatly within a small area, depending partly on the type and severity of the disturbance as well as on temporal factors such as water content and microbial activity. To date, many laboratory investigations into soil hydrophobicity have focused on smooth particle surfaces. As a result, our understanding of how hydrophobicity develops on rough surfaces of macro, micro and nano-particulates is limited; we are unable to predict with certainty how these soil particles will behave on contact with water. Surface chemistry is the main consideration when predicting hydrophobic behaviour of smooth solids, but for particles with rough surfaces, hydrophobicity is believed to develop as a combination of surface chemistry and topography. Topography may reflect both the arrangement (aggregation) of soil particles and the distribution of materials adsorbed on particulate surfaces. Patch-wise or complete coverage of rough soil particles by hydrophobic material may result in solid/water contact angles ≥150° , at which point the soil may be classified as super-hydrophobic. Here we present a critical review of the research to date on the effects of heterogeneity and surface roughness on soil hydrophobicity in which we discuss recent advances, current trends, and future research areas. References: Callies, M., Y. Chen, F. Marty, A. Pépin and D. Quéré. 2005. Microfabricated textured surfaces for super-hydrophobicity investigations. Microelectronic Engineering. 78-79:100-105. Doerr, S.H. C.J. Ritsema, L.W. Dekker, D.F. Scott and D. Carter. 2007. Water repellence of soils: new insights and emerging research needs. Hydrological Processes. 21:2223-2228. Doerr, S.H., R.A. Shakesby and R.P.D. Walsh. 2000. Soil water repellency: its causes, characteristics and hydro-geomorphological significance. Earth-Science Reviews. 51:33-65. McHale, G. N.J. Shirtcliffe, M.I. Newton, F.B. Pyatt and S.H. Doerr. 2007. Self-organization of hydrophobic soil and granular surfaces. Applied Physics Letters. 90. 054110.

Critical Synergistic Concentration of Lecithin Phospholipids Improves the Antimicrobial Activity of Eugenol against Escherichia coli.

PubMed

Zhang, Haoshu; Dudley, Edward G; Harte, Federico

2017-11-01

In this study, the effect of individual lecithin phospholipids on the antimicrobial properties of eugenol against Escherichia coli C600 was investigated. We tested five major phospholipids common in soy or egg lecithin (1,2-dihexadecanoyl-sn-glycero-3-phosphocholine [DPPC], 1,2-dioctadecanoyl-sn-glycero-3-phosphocholine [DSPC], 1,2-dihexadecanoyl-sn-glycero-3-phosphoethanolamine [DPPE], 1,2-dihexadecanoyl-sn-glycero-3-phosphate [sodium salt] [DPPA], and 1,2-dihexadecanoyl-sn-glycero-3-phospho-l-serine [DPPS]) and one synthetic cationic phospholipid (1,2-dioctadecanoyl-sn-glycero-3-ethylphosphocholine [18:0 EPC]). Among the six phospholipids, DPPC, DSPC, DPPE, DPPA, and the cationic 18:0 EPC showed critical synergistic concentrations that significantly improved the inactivation effect of eugenol against E. coli after 30 min of exposure. At the critical synergistic concentration, an additional ca. 0.4 to 1.9 log reduction (ca. 0.66 to 2.17 log CFU/ml reduction) in the microbial population was observed compared to eugenol-only (control) treatments (ca. 0.25 log reduction). In all cases, increasing the phospholipid amount above the critical synergistic concentration (which was different for each phospholipid) resulted in antimicrobial properties similar to those seen with the eugenol-only (control) treatments. DPPS did not affect the antimicrobial properties of eugenol at the tested concentrations. The critical synergistic concentration of phospholipids was correlated with their critical micelle concentrations (CMC). IMPORTANCE Essential oils (EOs) are naturally occurring antimicrobials, with limited use in food due to their hydrophobicity and strong aroma. Lecithin is used as a natural emulsifier to stabilize EOs in aqueous systems. We previously demonstrated that, within a narrow critical-concentration window, lecithin can synergistically enhance the antimicrobial properties of eugenol. Since lecithin is a mixture of different phospholipids, we aimed to identify which phospholipids are crucial for the observed synergistic effect. This research studied the bioactivity of lecithin phospholipids, contributing to a rational design in using lecithin to effectively control foodborne pathogens in foods. Copyright © 2017 American Society for Microbiology.

Green chromatography separation of analytes of greatly differing properties using a polyethylene glycol stationary phase and a low-toxic water-based mobile phase.

PubMed

Šatínský, Dalibor; Brabcová, Ivana; Maroušková, Alena; Chocholouš, Petr; Solich, Petr

2013-07-01

A simple, rapid, and environmentally friendly HPLC method was developed and validated for the separation of four compounds (4-aminophenol, caffeine, paracetamol, and propyphenazone) with different chemical properties. A "green" mobile phase, employing water as the major eluent, was proposed and applied to the separation of analytes with different polarity on polyethylene glycol (PEG) stationary phase. The chromatography separation of all compounds and internal standard benzoic acid was performed using isocratic elution with a low-toxicity mobile phase consisting of 0.04% (v/v) triethylamine and water. HPLC separation was carried out using a PEG reversed-phase stationary phase Supelco Discovery HS PEG column (15 × 4 mm; particle size 3 μm) at a temperature of 30 °C and flow rate at 1.0 mL min(-1). The UV detector was set at 210 nm. In this study, a PEG stationary phase was shown to be suitable for the efficient isocratic separation of compounds that differ widely in hydrophobicity and acid-base properties, particularly 4-aminophenol (log P, 0.30), caffeine (log P, -0.25), and propyphenazone (log P, 2.27). A polar PEG stationary phase provided specific selectivity which allowed traditional chromatographic problems related to the separation of analytes with different polarities to be solved. The retention properties of the group of structurally similar substances (aromatic amines, phenolic compounds, and xanthine derivatives) were tested with different mobile phases. The proposed green chromatography method was successfully applied to the analysis of active substances and one degradation impurity (4-aminophenol) in commercial preparation. Under the optimum chromatographic conditions, standard calibration was carried out with good linearity correlation coefficients for all compounds in the range (0.99914-0.99997, n = 6) between the peak areas and concentration of compounds. Recovery of the sample preparation was in the range 100 ± 5% for all compounds. The intraday method precision was determined as RSD, and the values were lower than 1.00%.

Determination of n-octanol/water partition coefficient for DDT-related compounds by RP-HPLC with a novel dual-point retention time correction.

PubMed

Han, Shu-ying; Qiao, Jun-qin; Zhang, Yun-yang; Yang, Li-li; Lian, Hong-zhen; Ge, Xin; Chen, Hong-yuan

2011-03-01

n-Octanol/water partition coefficients (P) for DDTs and dicofol were determined by reversed-phase high performance liquid chromatography (RP-HPLC) on a C(18) column using methanol-water mixture as mobile phase. A dual-point retention time correction (DP-RTC) was proposed to rectify chromatographic retention time (t(R)) shift resulted from stationary phase aging. Based on this correction, the relationship between logP and logk(w), the logarithm of the retention factor extrapolated to pure water, was investigated for a set of 12 benzene homologues and DDT-related compounds with reliable experimental P as model compounds. A linear regression logP=(1.10±0.04) logk(w) - (0.60±0.17) was established with correlation coefficient R(2) of 0.988, cross-validated correlation coefficient R(cv)(2) of 0.983 and standard deviation (SD) of 0.156. This model was further validated using four verification compounds, naphthalene, biphenyl, 2,2-bis(4-chlorophenyl)-1,1-dichloroethane (p,p'-DDD) and 2,2-bis(4-chlorophenyl)-1,1-dichloroethene (p,p'-DDE) with similar structure to DDT. The RP-HPLC-determined P values showed good consistency with shake-flask (SFM) or slow-stirring (SSM) results, especially for highly hydrophobic compounds with logP in the range of 4-7. Then, the P values for five DDT-related compounds, 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1,1-trichloroethane (o,p'-DDT), 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethane (o,p'-DDD), 2-(2-chlorophenyl)-2-(4-chlorophenyl)-1,1-dichloroethene (o,p'-DDE), and 2,2,2-trichloro-1,1-bis(4-chlorophenyl)ethanol (dicofol) and its main degradation product 4,4'-dichlorobenzophenone (p,p'-DBP) were evaluated by the improved RP-HPLC method for the first time. The excellent precision with SD less than 0.03 proved that the novel DP-RTC protocol can significantly increases the determination accuracy and reliability of P by RP-HPLC. Copyright © 2011 Elsevier Ltd. All rights reserved.

Polystyrene/wood composites and hydrophobic wood coatings from water-based hydrophilic-hydrophobic block copolymers

Treesearch

Marja-Leena Kosonen; Bo Wang; Gerard T. Caneba; Douglas J. Gardner; Tim G. Rials

2000-01-01

The combination of synthetic thermoplastic polymers and wood is normally problematic because wood surfaces are hydrophilic while typical thermoplastic polymers are hydrophobic. A possible solution is to use block copolymer coupling agents. In this work we show the use of a potentially useful synthetic method of producing hydrophilic-hydrophobic block copolymers as...

Method of separating and de-watering fine particles

DOEpatents

Yoon, Roe-Hoan

2016-12-13

A process for cleaning and dewatering hydrophobic particulate materials is presented. The process is performed in two steps: 1) agglomeration of the hydrophobic particles in a first hydrophobic liquid/aqueous mixture; followed by 2) dispersion of the agglomerates in a second hydrophobic liquid to release the water trapped within the agglomerates along with the entrained hydrophilic particles.

Combined hydrophobicity and mechanical durability through surface nanoengineering

DOE PAGES

Elliott, Paul R.; Stagon, Stephen P.; Huang, Hanchen; ...

2015-04-08

This paper reports combined hydrophobicity and mechanical durability through the nanoscale engineering of surfaces in the form of nanorod-polymer composites. Specifically, the hydrophobicity derives from nanoscale features of mechanically hard ZnO nanorods and the mechanical durability derives from the composite structure of a hard ZnO nanorod core and soft polymer shell. Experimental characterization correlates the morphology of the nanoengineered surfaces with the combined hydrophobicity and mechanical durability, and reveals the responsible mechanisms. Such surfaces may find use in applications, such as boat hulls, that benefit from hydrophobicity and require mechanical durability.

Challenges and solutions for biofiltration of hydrophobic volatile organic compounds.

PubMed

Cheng, Yan; He, Huijun; Yang, Chunping; Zeng, Guangming; Li, Xiang; Chen, Hong; Yu, Guanlong

2016-11-01

Volatile organic compounds (VOCs) emitted to the environment highly probably result in ecological and health risks. Many biotechnologies for waste gases containing hydrophobic VOCs have been developed in recent years. However, these biological processes usually exhibit poor removal performances for hydrophobic VOCs due to the low bioavailability. This review presents an overview of enhanced removal of hydrophobic VOCs in biofilters. Mechanisms and problems relevant to the biological removal of hydrophobic VOCs are reviewed, and then solutions including the addition of surfactants, application of fungal biocatalysts, biofiltration with pretreatment, innovative bioreactors and utilization of hydrophilic compounds are discussed in detail. Future research needs are also proposed. This review provides new insights into hydrophobic VOC removal by biofiltration. Copyright © 2016 Elsevier Inc. All rights reserved.

Pairwise-additive hydrophobic effect for alkanes in water

PubMed Central

Wu, Jianzhong; Prausnitz, John M.

2008-01-01

Pairwise additivity of the hydrophobic effect is indicated by reliable experimental Henry's constants for a large number of linear and branched low-molecular-weight alkanes in water. Pairwise additivity suggests that the hydrophobic effect is primarily a local phenomenon and that the hydrophobic interaction may be represented by a semiempirical force field. By representing the hydrophobic potential between two methane molecules as a linear function of the overlap volume of the hydration layers, we find that the contact value of the hydrophobic potential (−0.72 kcal/mol) is smaller than that from quantum mechanics simulations (−2.8 kcal/mol) but is close to that from classical molecular dynamics (−0.5∼−0.9 kcal/mol). PMID:18599448

Comparison between Free and Immobilized Ion Effects on Hydrophobic Interactions: A Molecular Dynamics Study.

PubMed

Huang, Kai; Gast, Sebastian; Ma, C Derek; Abbott, Nicholas L; Szlufarska, Izabela

2015-10-15

Fundamental studies of the effect of specific ions on hydrophobic interactions are driven by the need to understand phenomena such as hydrophobically driven self-assembly or protein folding. Using β-peptide-inspired nanorods, we investigate the effects of both free ions (dissolved salts) and proximally immobilized ions on hydrophobic interactions. We find that the free ion effect is correlated with the water density fluctuation near a nonpolar molecular surface, showing that such fluctuation can be an indicator of hydrophobic interactions in the case of solution additives. In the case of immobilized ion, our results demonstrate that hydrophobic interactions can be switched on and off by choosing different spatial arrangements of proximal ions on a nanorod. For globally amphiphilic nanorods, we find that the magnitude of the interaction can be further tuned using proximal ions with varying ionic sizes. In general, univalent proximal anions are found to weaken hydrophobic interactions. This is in contrast to the effect of free ions, which according to our simulations strengthen hydrophobic interactions. In addition, immobilized anions of increasing ionic size do not follow the same ordering (Hofmeister-like ranking) as free ions when it comes to their impact on hydrophobic interactions. The immobilized ion effect is not simply correlated with the water density fluctuation near the nonpolar side of the amphiphilic nanorod. We propose a molecular picture that explains the contrasting effects of immobilized versus free ions.

Chemical and colloidal aspects of collectorless flotation behavior of sulfide and non-sulfide minerals.

PubMed

Aghazadeh, Sajjad; Mousavinezhad, Seyed Kamal; Gharabaghi, Mahdi

2015-11-01

Flotation has been widely used for separation of valuable minerals from gangues based on their surface characterizations and differences in hydrophobicity on mineral surfaces. As hydrophobicity of minerals widely differs from each other, their separation by flotation will become easier. Collectors are chemical materials which are supposed to make selectively valuable minerals hydrophobic. In addition, there are some minerals which based on their surface and structural features are intrinsically hydrophobic. However, their hydrophobicities are not strong enough to be floatable in the flotation cell without collectors such as sulfide minerals, coal, stibnite, and so forth. To float these minerals in a flotation cell, their hydrophobicity should be increased in specific conditions. Various parameters including pH, Eh, size distribution, mill types, mineral types, ore characterization, and type of reaction in flotation cells affect the hydrophobicity of minerals. Surface analysis results show that when sulfide minerals experience specific flotation conditions, the reactions on the surface of these minerals increase the amount of sulfur on the surface. These phenomenons improve the hydrophobicity of these minerals due to strong hydrophobic feature of sulfurs. Collectorless flotation reduces chemical material consumption amount, increases flotation selectivity (grade increases), and affects the equipment quantities; however, it can also have negative effects. Some minerals with poor surface floatability can be increased by adding some ions to the flotation system. Depressing undesirable minerals in flotation is another application of collectorless flotation.

Albumin-Encapsulated Liposomes: A Novel Drug Delivery Carrier With Hydrophobic Drugs Encapsulated in the Inner Aqueous Core.

PubMed

Okamoto, Yuko; Taguchi, Kazuaki; Yamasaki, Keishi; Sakuragi, Mina; Kuroda, Shun'ichi; Otagiri, Masaki

2018-01-01

Liposomes are clinically used in drug delivery, but loading hydrophobic substances is limited to the hydrophobic space of a lipid membrane, despite the fact that it is favorable to encapsulate substances into the inner aqueous core of liposome, from a drug stability of view. We report herein on the preparation of a liposome with bovine serum albumin encapsulated (BSA-liposome). Using this system, it is possible to encapsulate hydrophobic drugs in the inner aqueous core of the liposome based on the hypothesis that the water solubility of hydrophobic drugs is increased when bound to albumin. The physicochemical properties of the prepared BSA-liposomes could be easily regulated and the loading of hydrophobic drugs in the inner aqueous core of the liposome was dramatically improved by virtue of the drug-binding properties of albumin. An in vivo safety and pharmacokinetic study showed that BSA-liposomes possess favorable properties as a drug carrier, including biocompatibility and a stealth effect. This new type of hydrophobic drug carrier, an albumin-liposome, has the potential for use in delivering numerous hydrophobic drugs that typically bind to albumin. Copyright © 2018 American Pharmacists Association®. Published by Elsevier Inc. All rights reserved.

Impact of wall hydrophobicity on condensation flow and heat transfer in silicon microchannels

NASA Astrophysics Data System (ADS)

Fang, Chen; Steinbrenner, Julie E.; Wang, Fu-Min; Goodson, Kenneth E.

2010-04-01

While microchannel condensation has been the subject of several recent studies, the critical impact of wall hydrophobicity on the microchannel condensation flow has received very little attention. The paper experimentally studies steam condensation in a silicon microchannel 286 µm in hydraulic diameter with three different wall hydrophobicities. It is found that the channel surface wettability has a significant impact on the flow pattern, pressure drop and heat transfer characteristic. Spatial flow pattern transition is observed in both hydrophobic and hydrophilic channels. In the hydrophobic channel, the transition from dropwise/slugwise flow to plug flow is induced by the slug instability. In the hydrophilic channel, the flow transition is characterized by the periodic bubble detachment, a process in which pressure evolution is found important. Local temperature measurement is conducted and heat flux distribution in the microchannel is reconstructed. For the same inlet vapor flux and temperature, the hydrophobic microchannel yields higher heat transfer rate and pressure drop compared to the hydrophilic channel. The difference is attributed to the distinction in flow pattern and heat transfer mechanism dictated by the channel hydrophobicity. This study highlights the importance of the channel hydrophobicity control for the optimization of the microchannel condenser.

Soft matter interactions at the molecular scale: interaction forces and energies between single hydrophobic model peptides.

PubMed

Stock, Philipp; Utzig, Thomas; Valtiner, Markus

2017-02-08

In all realms of soft matter research a fundamental understanding of the structure/property relationships based on molecular interactions is crucial for developing a framework for the targeted design of soft materials. However, a molecular picture is often difficult to ascertain and yet essential for understanding the many different competing interactions at play, including entropies and cooperativities, hydration effects, and the enormous design space of soft matter. Here, we characterized for the first time the interaction between single hydrophobic molecules quantitatively using atomic force microscopy, and demonstrated that single molecular hydrophobic interaction free energies are dominated by the area of the smallest interacting hydrophobe. The interaction free energy amounts to 3-4 kT per hydrophobic unit. Also, we find that the transition state of the hydrophobic interactions is located at 3 Å with respect to the ground state, based on Bell-Evans theory. Our results provide a new path for understanding the nature of hydrophobic interactions at the single molecular scale. Our approach enables us to systematically vary hydrophobic and any other interaction type by utilizing peptide chemistry providing a strategic advancement to unravel molecular surface and soft matter interactions at the single molecular scale.

Super-Hydrophobic Surface Prepared by Lanthanide Oxide Ceramic Deposition Through PS-PVD Process

NASA Astrophysics Data System (ADS)

Li, Jie; Li, Cheng-Xin; Chen, Qing-Yu; Gao, Jiu-Tao; Wang, Jun; Yang, Guan-Jun; Li, Chang-Jiu

2017-02-01

Super-hydrophobic surface has received widespread attention in recent years. Both the surface morphology and chemical composition have significant impact on hydrophobic performance. A novel super-hydrophobic surface based on plasma spray-vapor deposition was introduced in the present paper. Samaria-doped ceria, which has been proved as an intrinsic hydrophobic material, was used as feedstock material. Additionally, in order to investigate the influence of surface free energy on the hydrophobicity, chemical modification by low surface free energy materials including stearic acid and 1,1,2,2-tetrahydroperfluorodecyltrimethoxysilane (FAS) was used on coating surface. Scanning electron microscopy and Fourier transform infrared spectroscopy were employed to characterize the coating surface. The results show that the obtained surface has a hierarchical structure composed by island-like structures agglomerated with angular-like sub-micrometer-sized particles. Moreover, with the surface free energy decreases, the hydrophobic property of the surface improves gradually. The water contact angle of the as-sprayed coating surface increases from 110° to 148° after modification by stearic acid and up to 154° by FAS. Furthermore, the resultant surface with super-hydrophobicity exhibits an excellent stability.

Wear resistance of hydrophobic surfaces

NASA Astrophysics Data System (ADS)

Martinez, MA; Abenojar, J.; Pantoja, M.; López de Armentia, S.

2017-05-01

Nature has been an inspiration source to develop artificial hydrophobic surfaces. During the latest years the development of hydrophobic surfaces has been widely researched due to their numerous ranges of industrial applications. Industrially the use of hydrophobic surfaces is being highly demanded. This is why many companies develop hydrophobic products to repel water, in order to be used as coatings. Moreover, these coating should have the appropriated mechanical properties and wear resistance. In this work wear study of a hydrophobic coating on glass is carried out. Hydrophobic product used was Sika Crystal Dry by Sika S.A.U. (Alcobendas, Spain). This product is currently used on car windshield. To calculate wear resistance, pin-on-disk tests were carried out in dry and water conditions. The test parameters were rate, load and sliding distance, which were fixed to 60 rpm, 5 N and 1000 m respectively. A chamois was used as pin. It allows to simulate a real use. The friction coefficient and loss weight were compared to determinate coating resistance

Separation of proteins by hydrophobic interaction chromatography at low salt concentration.

PubMed

Kato, Yoshio; Nakamura, Koji; Kitamura, Takashi; Moriyama, Hiroyuki; Hasegawa, Masazumi; Sasaki, Hiroo

2002-09-20

We investigated protein separation by hydrophobic interaction chromatography (HIC) at low salt concentration on the supports of various hydrophobicities. Hydrophobic proteins could be successfully separated with more than 90% recovery by gradient elution of ammonium sulfate from 0.3-0.5 M to 0 in 50 mM phosphate buffer (pH 6.8) by using supports whose hydrophobicities were properly adjusted individually for each protein. Satisfactory results were also obtained by isocratic elution without ammonium sulfate and gradient elution of ethanol from 0 to 10%. HIC at low salt concentration was compatible with other modes of liquid chromatography like ion-exchange chromatography. On the other hand, it was not successful to separate hydrophilic proteins at low salt concentration. Recoveries of hydrophilic proteins decreased before they were retained enough as support hydrophobicity increased. Therefore, it is inevitable to use a higher concentration of salt, e.g., 1-2 M ammonium sulfate, on hydrophilic or moderately hydrophobic support in order to retain hydrophilic proteins without decrease in recovery.

Condensation Dynamics on Mimicked Metal Matrix Hydrophobic Nanoparticle-Composites

NASA Astrophysics Data System (ADS)

Damle, Viraj; Sun, Xiaoda; Rykaczewski, Konrad

2014-11-01

Use of hydrophobic surfaces promotes condensation in the dropwise mode, which is significantly more efficient than the common filmwise mode. However, limited longevity of hydrophobic surface modifiers has prevented their wide spread use in industry. Recently, metal matrix composites (MMCs) having microscale hydrophobic heterogeneities dispersed in hydrophilic metal matrix have been proposed as durable and self-healing alternative to hydrophobic surface coatings interacting with deposited water droplets. While dispersion of hydrophobic microparticles in MMC is likely to lead to surface flooding during condensation, the effect of dispersion of hydrophobic nanoparticles (HNPs) with size comparable to water nuclei critical radii and spacing is not obvious. To this end, we fabricated highly ordered arrays of Teflon nanospheres on silicon substrates that mimic the top surface of the MMCs with dispersed HNPs. We used light and electron microscopy to observe breath figures resulting from condensation on these surfaces at varied degrees of subcooling. Here, we discuss the relation between the droplet size distribution, Teflon nanosphere diameter and spacing, and condensation mode. KR acknowledges startup funding from ASU.

Super-hydrophobic surfaces of SiO₂-coated SiC nanowires: fabrication, mechanism and ultraviolet-durable super-hydrophobicity.

PubMed

Zhao, Jian; Li, Zhenjiang; Zhang, Meng; Meng, Alan

2015-04-15

The interest in highly water-repellent surfaces of SiO2-coated SiC nanowires has grown in recent years due to the desire for self-cleaning and anticorrosive surfaces. It is imperative that a simple chemical treatment with fluoroalkylsilane (FAS, CF3(CF2)7CH2CH2Si(OC2H5)3) in ethanol solution at room temperature resulted in super-hydrophobic surfaces of SiO2-coated SiC nanowires. The static water contact angle of SiO2-coated SiC nanowires surfaces was changed from 0° to 153° and the morphology, microstructure and crystal phase of the products were almost no transformation before and after super-hydrophobic treatment. Moreover, a mechanism was expounded reasonably, which could elucidate the reasons for their super-hydrophobic behavior. It is important that the super-hydrophobic surfaces of SiO2-coated SiC nanowires possessed ultraviolet-durable (UV-durable) super-hydrophobicity. Copyright © 2014 Elsevier Inc. All rights reserved.

BODIPY-Based Fluorescent Probes for Sensing Protein Surface-Hydrophobicity.

PubMed

Dorh, Nethaniah; Zhu, Shilei; Dhungana, Kamal B; Pati, Ranjit; Luo, Fen-Tair; Liu, Haiying; Tiwari, Ashutosh

2015-12-18

Mapping surface hydrophobic interactions in proteins is key to understanding molecular recognition, biological functions, and is central to many protein misfolding diseases. Herein, we report synthesis and application of new BODIPY-based hydrophobic sensors (HPsensors) that are stable and highly fluorescent for pH values ranging from 7.0 to 9.0. Surface hydrophobic measurements of proteins (BSA, apomyoglobin, and myoglobin) by these HPsensors display much stronger signal compared to 8-anilino-1-naphthalene sulfonic acid (ANS), a commonly used hydrophobic probe; HPsensors show a 10- to 60-fold increase in signal strength for the BSA protein with affinity in the nanomolar range. This suggests that these HPsensors can be used as a sensitive indicator of protein surface hydrophobicity. A first principle approach is used to identify the molecular level mechanism for the substantial increase in the fluorescence signal strength. Our results show that conformational change and increased molecular rigidity of the dye due to its hydrophobic interaction with protein lead to fluorescence enhancement.

A study of degradation resistance and cytocompatibility of super-hydrophobic coating on magnesium.

PubMed

Zhang, Yufen; Feyerabend, Frank; Tang, Shawei; Hu, Jin; Lu, Xiaopeng; Blawert, Carsten; Lin, Tiegui

2017-09-01

Calcium stearate based super-hydrophobic coating was deposited on plasma electrolytic oxidation (PEO) pre-treated magnesium substrate. The pre-treated magnesium and super-hydrophobic coating covered sample were characterized by scanning electron microscopy, X-ray diffraction and electrochemical corrosion measurements. The cytocompatibility and degradation resistance of magnesium, pre-treated magnesium and super-hydrophobic coating were analysed in terms of cell adhesion and osteoblast differentiation. The results indicate that the calcium stearate top coating shows super-hydrophobicity and that the surface is composed of micro/nanostructure. The super-hydrophobic coating covered sample shows higher barrier properties compared with the PEO pre-treated magnesium and bare magnesium. Human osteoblast proliferation, but not differentiation is enhanced by the PEO coating. Contrary, the super-hydrophobic coating reduces proliferation, but enhances differentiation of osteoblast, observable by the formation of hydroxyapatite. The combination of corrosion protection and cell reaction indicates that this system could be interesting for biomedical applications. Copyright © 2017 Elsevier B.V. All rights reserved.