Many semi-volatile organic compounds (SVOCs) accumulate in indoor dust, which serves as a repository for those compounds. The presence of SVOCs in indoor environments is of concern because many of them are suspected to have toxic effects. Total SVOC concentrations in the dust are generally used for exposure assessment to indoor contaminants, assuming that 100% of the SVOCs is accessible for human uptake. However, such an assumption may potentially lead to an overestimated risk related to dust exposure. We applied a multi-ratio equilibrium passive sampling (MR-EPS) for estimation of SVOC accessibility in indoor settled dust using silicone passive samplers and three particle size dust fractions, <0.25 mm, 0.25-0.5 mm, and 1-2 mm in dry and wet conditions. Equilibrations were performed at various sampler-dust mass ratios to achieve different degrees of SVOC depletion, allowing the construction of a desorption isotherm. The desorption isotherms provided accessible fractions (FAS), equivalent air concentrations (CAIR), dust-air partition coefficients (KDUST-AIR) and organic carbon-air partition coefficients (KOC-AIR). The highest FAS were observed in the <0.25 mm dust fraction in wet conditions which is relevant for exposure assessment via oral ingestion. The highest CAIR were estimated for several organophosphorus flame retardants (OPFRs), polycyclic aromatic hydrocarbons (PAHs) and synthetic musks. The logKOC-AIR did not differ between dust particle sizes in dry and wet conditions but within compound groups, different relationships with hydrophobicity were observed. Equivalent lipid-based concentrations (CL⇌DUST) calculated using available lipid-silicone partition coefficients (KLIP-SIL) were compared with lipid-based concentrations (CL) measured in human-related samples collected from Europeans. For hexachlorobenzene (HCB), CL⇌DUST, and CL were similar, indicating equilibrium attainment between environment and human samples. Lipid-based concentrations for persistent legacy contaminants were also similar but lower for PBDEs in human samples. Overall, accessibility estimation using MR-EPS in dust further contributes to human risk assessment.
- MeSH
- Risk Assessment MeSH
- Humans MeSH
- Lipids MeSH
- Environmental Monitoring MeSH
- Dust analysis MeSH
- Flame Retardants * analysis MeSH
- Volatile Organic Compounds * analysis MeSH
- Air Pollution, Indoor * analysis MeSH
- Check Tag
- Humans MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
Encapsulation into liposomes is a formulation strategy that can improve efficacy and reduce side effects of active pharmaceutical ingredients (APIs) that exhibit poor biodistribution or pharmacokinetics when administered alone. However, many APIs are unsuitable for liposomal formulations intended for parenteral administration due to their inherent physicochemical properties─lipid bilayer permeability and water-lipid equilibrium partitioning coefficient. Too high permeability results in premature leakage from liposomes, while too low permeability means the API is not able to pass across biological barriers. There are several options for solving this issue: (i) change of the lipid bilayer composition, (ii) addition of a permeability enhancer, or (iii) modification of the chemical structure of the API to design a prodrug. The latter approach was taken in the present work, and the effect of small changes in the molecular structure of the API on its permeation rate across a lipidic bilayer was systematically explored utilizing computer simulations. An in silico methodology for prodrug design based on the COSMOperm approach has been proposed and applied to four APIs (abiraterone, cytarabine, 5-fluorouracil, and paliperidone). It is shown that the addition of aliphatic hydrocarbon chains via ester or amide bonds can render the molecule more lipophilic and increase its permeability by approximately 1 order of magnitude for each 2 carbon atoms added, while the formation of fructose adducts can provide a more hydrophilic character to the molecule and reduce its lipid partitioning. While partitioning was found to depend only on the size and type of the added group, permeability was found to depend also on the added group location. Overall, it has been shown that both permeability and lipid partitioning coefficient can be systematically shifted into the desired liposome formulability window by appropriate group contributions to the parental drug. This can significantly increase the portfolio of APIs for which liposome or lipid nanoparticle formulations become feasible.
This paper presents experimental results from the use of biosurfactants in the remediation of a soil from a smelter in Poland. In the soil, concentrations of Cu (1659.1 mg/kg) and Pb (290.8 mg/kg) exceeded the limit values. Triple batch washing was tested as a soil treatment. Three main variants were used, each starting with a different plant-derived (saponin, S; tannic acid, T) or microbial (rhamnolipids, R) biosurfactant solution in the first washing, followed by 9 different sequences using combinations of the tested biosurfactants (27 in total). The efficiency of the washing was determined based on the concentration of metal removed after each washing (CR), the cumulative removal efficiency (Ecumulative) and metal stability (calculated as the reduced partition index, Ir, based on the metal fractions from BCR sequential extraction). The type of biosurfactant sequence influenced the CR values. The variants that began with S and R had the highest average Ecumulative for Cu and Pb, respectively. The Ecumulative value correlated very strongly (r > 0.8) with the stability of the residual metals in the soil. The average Ecumulative and stability of Cu were the highest, 87.4% and 0.40, respectively, with the S-S-S, S-S-T, S-S-R and S-R-T sequences. Lead removal and stability were the highest, 64-73% and 0.36-0.41, respectively, with the R-R-R, R-R-S, R-S-R and R-S-S sequences. Although the loss of biosurfactants was below 10% after each washing, sequential washing with biosurfactants enriched the soil with external organic carbon by an average of 27-fold (S-first variant), 24-fold (R first) or 19-fold (T first). With regard to environmental limit values, metal stability and organic carbon resources, sequential washing with different biosurfactants is a beneficial strategy for the remediation of smelter-contaminated soil with given properties.
- MeSH
- Soil Pollutants * analysis MeSH
- Soil MeSH
- Environmental Restoration and Remediation * MeSH
- Metals, Heavy * analysis MeSH
- Environmental Pollution MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
- Geographicals
- Poland MeSH
Fungal metabolic carbon acquisition and its subsequent partitioning between biomass production and respiration, i.e. the carbon-use efficiency (CUE), are central parameters in biogeochemical modeling. However, current available techniques for estimating these parameters are all associated with practical and theoretical shortcomings, making assessments unreliable. Gene expression analyses hold the prospect of phenotype prediction by indirect means, providing new opportunities to obtain information about metabolic priorities. We cultured four different fungal isolates (Chalara longipes, Laccaria bicolor, Serpula lacrymans and Trichoderma harzianum) in liquid media with contrasting nitrogen availability and measured growth rates and respiration to calculate CUE. By relating gene expression markers to measured carbon fluxes, we identified genes coding for 1,3-β-glucan synthase and 2-oxoglutarate dehydrogenase as suitable markers for growth and respiration, respectively, capturing both intraspecific variation as well as within-strain variation dependent on growth medium. A transcript index based on these markers correlated significantly with differences in CUE between the fungal isolates. Our study paves the way for the use of these markers to assess differences in growth, respiration and CUE in natural fungal communities, using metatranscriptomic or the RT-qPCR approach.
- MeSH
- Ascomycota genetics metabolism MeSH
- Basidiomycota genetics MeSH
- Biomarkers * analysis MeSH
- Fungal Proteins * genetics metabolism MeSH
- Fungi * genetics metabolism MeSH
- Hypocreales genetics metabolism MeSH
- Laccaria genetics metabolism MeSH
- Transcriptome * MeSH
- Trichoderma genetics metabolism MeSH
- Carbon * metabolism MeSH
- Publication type
- Journal Article MeSH
- Research Support, Non-U.S. Gov't MeSH
Leaf senescence, accompanied by chlorophyll breakdown, chloroplast degradation and inhibition of photosynthesis, can be suppressed by an exogenous application of cytokinins. Two aromatic cytokinin arabinosides (6-benzylamino-9-β-d-arabinofuranosylpurines; BAPAs), 3-hydroxy- (3OHBAPA) and 3-methoxy- (3MeOBAPA) derivatives, have recently been found to possess high anti-senescence activity. Interestingly, their effect on the maintenance of chlorophyll content and maximal quantum yield of photosystem II (PSII) in detached dark-adapted leaves differed quantitatively in wheat (Triticum aestivum L. cv. Aranka) and Arabidopsis (Arabidopsisthaliana L. (Col-0)). In this work, we have found that the anti-senescence effects of 3OHBAPA and 3MeOBAPA in wheat and Arabidopsis also differ in other parameters, including the maintenance of carotenoid content and chloroplasts, rate of reduction of primary electron acceptor of PSII (QA) as well as electron transport behind QA, and partitioning of absorbed light energy in light-adapted leaves. In wheat, 3OHBAPA had a higher protective effect than 3MeOBAPA, whereas in Arabidopsis, 3MeOBAPA was the more efficient derivative. We have found that the different anti-senescent activity of 3OHBAPA and 3MeOBAPA was coupled to different ethylene production in the treated leaves: the lower the ethylene production, the higher the anti-senescence activity. 3OHBAPA and 3MeOBAPA also efficiently protected the senescing leaves of wheat and Arabidopsis against oxidative damage induced by both H2O2 and high-light treatment, which could also be connected with the low level of ethylene production.
- MeSH
- Arabidopsis drug effects growth & development metabolism MeSH
- Cytokinins pharmacology MeSH
- Ethylenes metabolism MeSH
- Photosynthesis MeSH
- Plant Leaves drug effects growth & development metabolism MeSH
- Triticum drug effects growth & development metabolism MeSH
- Plant Growth Regulators pharmacology MeSH
- Cellular Senescence * MeSH
- Publication type
- Journal Article MeSH
Total concentrations of hydrophobic organic contaminants (HOCs) in sediment present a poor quality assessment parameter for aquatic organism exposure and environmental risk because they do not reflect contaminant bioavailability. The bioavailability issue of HOCs in sediments can be addressed by application of multi-ratio equilibrium passive sampling (EPS). In this study, riverbed sediment samples were collected during the Joint Danube Survey at 9 locations along the Danube River in 2013. Samples were ex-situ equilibrated with silicone passive samplers. Desorption isotherms were constructed, yielding two endpoints: pore water (CW:0) and accessible (CAS:0) concentration of polychlorinated biphenyls (PCBs), organochlorine pesticides (OCPs), polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers in sediment. CW:0 concentrations of DDT and its breakdown products exhibited elevated levels in the low Danube, with the maximum in the river delta. Other investigated HOCs did not show any clear spatial trends along the river, and only a moderate CW:0 variability. CAS:0 in sediment ranged from 10 to 90% of the total concentration in sediment. CW:0 was compared with freely dissolved concentration in the overlaying surface water, measured likewise by passive sampling. The comparison indicated potential compound release from sediment to the water phase for PAHs with less than four aromatic rings, and for remaining HOCs either equilibrium between sediment and water, or potential compound deposition in sediment. Sorption partition coefficients of HOC to organic carbon correlated well with octanol-water partition coefficients (KOW), showing stronger sorption of PAHs to sediment than that of PCBs and OCPs having equal logKOW. Comparison of CW:0 values with European environmental quality standards indicated potential exceedance for hexachlorobenzene, fluoranthene and benzo[a]pyrene at several sites. The study demonstrates the utility of passive sampling as an innovative approach for risk-oriented monitoring of HOCs in river catchments.
Topsoils near active and abandoned mining and smelting sites are highly polluted by metal(loid) contaminants, which are often bound to particulates emitted from ore processing facilities and/or windblown from waste disposal sites. To quantitatively determine the contaminant partitioning in the soil particulates, we tested an automated mineralogy approach on the heavy mineral fraction extracted from the mining- and smelting-polluted topsoils exhibiting up to 1920 mg/kg As, 5840 mg/kg Cu, 4880 mg/kg Pb and 3310 mg/kg Zn. A new generation of automated scanning electron microscopy (autoSEM) was combined and optimized with conventional mineralogical techniques (XRD, SEM/EDS, EPMA). Parallel digestions and bulk chemical analyses were used as an independent control of the autoSEM-calculated concentrations of the key elements. This method provides faster data acquisition, the full integration of the quantitative EDS data and better detection limits for the elements of interest. We found that As was mainly bound to the apatite group minerals, slag glass and metal arsenates. Copper was predominantly hosted by the sulfides/sulfosalts and the Cu-bearing secondary carbonates. The deportment of Pb is relatively complex: slag glass, Fe and Mn (oxyhydr)oxides, metal arsenates/vanadates and cerussite were the most important carriers for Pb. Zinc is mainly bound to the slag glass, Fe (oxyhydr)oxides, smithsonite and sphalerite. Limitations exist for the less abundant contaminants, which cannot be fully quantified by autoSEM due to spectral overlaps with some major elements (e.g., Sb vs. Ca, Cd vs. K and Ca in the studied soils). AutoSEM was found to be a useful tool for the determination of the modal phase distribution and element partitioning in the metal(loid)-bearing soil particulates and will definitely find more applications in environmental soil sciences in the future.
- MeSH
- Mining MeSH
- Soil Pollutants analysis MeSH
- Minerals analysis MeSH
- Environmental Monitoring MeSH
- Soil MeSH
- Metals, Heavy analysis MeSH
- Publication type
- Journal Article MeSH
We suggest a new technique for estimating the relative drawdown of CO2 concentration (c) in the intercellular air space (IAS) across hypostomatous leaves (expressed as the ratio cd/cb, where the indexes d and b denote the adaxial and abaxial edges, respectively, of IAS), based on the carbon isotope composition (δ13C) of leaf cuticular membranes (CMs), cuticular waxes (WXs) or epicuticular waxes (EWXs) isolated from opposite leaf sides. The relative drawdown in the intracellular liquid phase (i.e., the ratio cc/cbd, where cc and cbd stand for mean CO2 concentrations in chloroplasts and in the IAS), the fraction of intercellular resistance in the total mesophyll resistance (rIAS/rm), leaf thickness, and leaf mass per area (LMA) were also assessed. We show in a conceptual model that the upper (adaxial) side of a hypostomatous leaf should be enriched in 13C compared to the lower (abaxial) side. CM, WX, and/or EWX isolated from 40 hypostomatous C3 species were 13C depleted relative to bulk leaf tissue by 2.01-2.85‰. The difference in δ13C between the abaxial and adaxial leaf sides (δ13CAB - 13CAD, Δb-d), ranged from - 2.22 to + 0.71‰ (- 0.09 ± 0.54‰, mean ± SD) in CM and from - 7.95 to 0.89‰ (- 1.17 ± 1.40‰) in WX. In contrast, two tested amphistomatous species showed no significant Δb-d difference in WX. Δb-d correlated negatively with LMA and leaf thickness of hypostomatous leaves, which indicates that the mesophyll air space imposes a non-negligible resistance to CO2 diffusion. δ13C of EWX and 30-C aldehyde in WX reveal a stronger CO2 drawdown than bulk WX or CM. Mean values of cd/cb and cc/cbd were 0.90 ± 0.12 and 0.66 ± 0.11, respectively, across 14 investigated species in which wax was isolated and analyzed. The diffusion resistance of IAS contributed 20 ± 14% to total mesophyll resistance and reflects species-specific and environmentally-induced differences in leaf functional anatomy.
- MeSH
- Models, Biological MeSH
- Extracellular Space metabolism MeSH
- Carbon Isotopes metabolism MeSH
- Plant Leaves anatomy & histology growth & development metabolism MeSH
- Mesophyll Cells metabolism MeSH
- Altitude MeSH
- Carbon Dioxide metabolism MeSH
- Waxes metabolism MeSH
- Publication type
- Journal Article MeSH
The dissipation, partitioning dynamics and biouptake was measured for selected hazardous current-used pesticides (conazole fungicides: epoxiconazole, flusilazole, tebuconazole; prochloraz, chlorpyrifos, pendimethalin) and for a transformation product (2-hydroxyatrazine) in agricultural soil and quartz sand as representatives of a real and a worst-case scenario. Dissipation, uptake to Lactuca sativa and the freely dissolved concentration along with the organic carbon-normalized sorption coefficients (Koc) were determined on days 12, 40, and 90 following the application of compounds at three fortification levels (0.1-1.0-10 mg/kg). Conazole fungicides showed similar dissipation patterns and were more persistent in soil than prochloraz, chlorpyrifos and pendimethalin. 2-Hydroxyatrazine showed a concentration-depended decrease in persistency in soil. Lettuce roots were shown to accumulate higher amounts than shoots where the extent of root uptake was driven by compound partitioning. This was evidenced by the ability of freely dissolved concentration (Cfree) to reliably (r2 = 0.94) predict root uptake. Concentration in leaves did not exceed the maximum residue levels (MRLs) for lettuce, which was likely given by the low root-to-shoot translocation factors (TFs) of the tested compounds varying between 0.007 and 0.14. Koc values were in the range of literature values. Sorption to soil was higher than to sand for all compounds, yet following the Koc dynamics compounds did not appear to be sequestered in soil with increasing residence time. From these results, it follows that the tested compounds may persist in soil but since they did not accumulate in lettuce above MRLs, contamination of the food web is unlikely.
- MeSH
- Atrazine analogs & derivatives analysis pharmacokinetics MeSH
- Plant Roots metabolism MeSH
- Soil Pollutants analysis MeSH
- Plant Leaves metabolism MeSH
- Pesticides analysis pharmacokinetics MeSH
- Fungicides, Industrial analysis pharmacokinetics MeSH
- Lactuca metabolism MeSH
- Publication type
- Journal Article MeSH
Reclamation of post-mining sites commonly results in rapid accrual of carbon (C) and nitrogen (N) contents due to increasing plant inputs over time. However, little information is available on the distribution of C and N contents with respect to differently stabilized soil organic matter (SOM) fractions during succession or as a result of different reclamation practice. Hence, it remains widely unknown how stable or labile these newly formed C and N pools are. Gaining a deeper understanding of the state of these pools may provide important implications for reclamation practices with respect to C sequestration. We thus investigated C, N, and plant-derived compounds in bulk soil and SOM fractions during succession in post-mining chronosequences (reclaimed with overburden or salvaged topsoil) located along a northwest to southeast transect across the USA. Our results indicate that current reclamation practices perform well with respect to rapid recovery of soil aggregates and the partitioning of C and N to different SOM fractions, these measures being similar to those of natural climax vegetation sites already 2-5 years after reclamation. A general applicability of our results to other post-mining sites with similar reclamation practices may be inferred from the fact that the observed patterns were consistent along the investigated transect, covering different climates and vegetation across the USA. However, regarding SOM stability, the use of salvaged topsoil may be beneficial as compared to that of overburden material because C and N in the fraction regarded as most stable was by 26 and 35% lower at sites restored with overburden as compared to those restored with salvaged topsoil. Plant-derived compounds appeared to be mainly related to bio-available particulate organic matter and particulate organic matter partly stabilized within aggregates, challenging the long-term persistence of plant input C in post-mining soils.
