Molecular signatures of organic particulates as tracers of emission sources

Chemical signature of airborne particulates and deposition dusts is subject of study since decades. Usually, three complementary composition markers are investigated, namely, (i) specific organic compounds; (ii) concentration ratios between congeners, and (iii) percent distributions of homologs. Due to its intrinsic limits (e.g., variability depending on decomposition and gas/particle equilibrium), the identification of pollution sources based on molecular signatures results overall restricted to qualitative purposes. Nevertheless, chemical fingerprints allow drawing preliminary information, suitable for successfully approaching multivariate analysis and valuing the relative importance of sources. Here, the state-of-the-art is presented about the molecular fingerprints of non-polar aliphatic, polyaromatic (PAHs, nitro-PAHs), and polar (fatty acids, organic halides, polysaccharides) compounds in emissions. Special concern was addressed to alkenes and alkanes with carbon numbers ranging from 12 to 23 and?≥?24, which displayed distinct relative abundances in petrol-derived spills and exhausts, emissions from microorganisms, high vegetation, and sediments. Long-chain alkanes associated with tobacco smoke were characterized by a peculiar iso/anteiso/normal homolog fingerprint and by n-hentriacontane percentages higher than elsewhere. Several concentration ratios of PAHs were identified as diagnostic of the type of emission, and the sources of uncertainty were elucidated. Despite extensive investigations conducted so far, the origin of uncommon molecular fingerprints, e.g., alkane/alkene relationships in deposition dusts and airborne particles, remains quite unclear. Polar organics resulted scarcely investigated for pollution apportioning purposes, though they looked as indicative of the nature of sources. Finally, the role of humans and living organisms as actual emitters of chemicals seems to need concern in the future.

     

Molecular properties of a fermented manure preparation used as field spray in biodynamic agriculture

Manure products fermented underground in cow horns and commonly used as field spray (preparation 500) in the biodynamic farming system, were characterized for molecular composition by solid-state nuclear magnetic resonance [¹³?C cross-polarization magic-angle-spinning NMR (¹³?C-CPMAS-NMR)] spectroscopy and offline tetramethylammonium hydroxide thermochemolysis gas chromatography-mass spectrometry. Both thermochemolysis and NMR spectroscopy revealed a complex molecular structure, with lignin aromatic derivatives, polysaccharides, and alkyl compounds as the predominant components. CPMAS-NMR spectra of biodynamic preparations showed a carbon distribution with an overall low hydrophobic character and significant contribution of lignocellulosic derivatives. The results of thermochemolysis confirmed the characteristic highlighted by NMR spectroscopy, revealing a molecular composition based on alkyl components of plant and microbial origin and the stable incorporation of lignin derivatives. The presence of biolabile components and of undecomposed lignin compounds in the preparation 500 should be accounted to its particularly slow maturation process, as compared to common composting procedures. Our results provide, for the first time, a scientific characterization of an essential product in biodynamic agriculture, and show that biodynamic products appear to be enriched of biolabile components and, therefore, potentially conducive to plant growth stimulation.     

Molecular size distribution of compost-derived humates as a function of concentration and different counterions

Conformational changes in the structures of humic acids (HA) extracted from compost with varying degrees of maturity were monitored by high performance size exclusion chromatography (HPSEC). The molecular size distribution of HA was compared in solutions containing sodium or ammonium counterions at pH 7 and pH 4.5. These findings indicate that the humates' molecular size depended not only on the nature of the counterions but also on their concentration in the solution. The physicochemical nature of sodium counterions determined smaller molecular sizes than those of the more hydrated ammonium counterions, at low concentrations of humates. Conversely, at higher humate concentrations, the more compact conformation of sodium humates produced larger molecular sizes than those of ammonium humates due to the aggregation of more hydrophobic surfaces in the sodium humates. Composting led to the degradation of labile microbial components with accumulation of hydrophobic constituents. This caused self-association of hydrophobic compounds into humic superstructures of larger molecular size over composting time. At lower pH, changes in conformational stability by the addition of acetic acid to humate solutions were explained by the supramolecular model of humified organic matter.     

Occurrence and suitability of pharmaceuticals and personal care products as molecular markers for raw wastewater contamination in surface water and groundwater

This study aimed to provide the first and comprehensive data on the occurrence of 17 target pharmaceuticals and personal care products (PPCPs) in urban water environment in Singapore. Meanwhile, this study also verified the suitability of these PPCPs as specific markers of raw wastewater contamination in receiving water bodies in highly urbanized areas where both surface water and groundwater are not impacted by the discharge of treated wastewater effluents. Analytical results of wastewater showed that among 17 target PPCPs examined, only 5 PPCPs were detected in 100 % of raw wastewater samples, including acetaminophen (ACT), carbamazepine (CBZ), caffeine (CF), diethyltoluamide (DEET), and salicylic acid (SA). Similarly, these PPCPs were found in most surface water and groundwater. Interestingly, the three PPCPs (ACT, CBZ, and SA) were only detected in surface water and groundwater in the sampling sites close to relatively older sewer systems, while they were absent in background samples that were collected from the catchment with no known wastewater sources. This suggests that ACT, CBZ, and SA can be used as specific molecular markers of raw wastewater in surface water and groundwater. This study also confirmed that CF and DEET were not really associated with wastewater sources, thus cannot serve well as specific molecular markers of wastewater contamination in receiving water bodies. To the best knowledge of the authors, the use of ACT and SA as specific molecular markers of raw wastewater contamination in urban surface waters and groundwater was first reported. Further studies on the use of ACT, CBZ, and SA along with other chemical/microbial markers are recommended to identify and differentiate contamination sources of surface waters/groundwater.     

Exotic gene expression in transgenic plants as a tool for monitoring environmental pollution

Environmental monitoring can benefit from the application of molecular and biochemical techniques as biomarkers. In principle, molecular biomarkers may have some advantage over more classical, organismal level markers because of their sensitivity, efficiency and reproducibility. Nevertheless, some disadvantages such as the cost, resource requirements and lack of specificity have limited their widespread use. Molecular genetics and recombinant DNA technologies, however, allow to improve simplicity and cost, together with reliability, efficiency and sensitivity, of molecular biomarkers. The stress inducible promoter of the barley gene Hvhspl7, which is induced by a number of environmental stress (including some heavy metals), has been fused to the reporter gene GUS in a plasmid. This plasmid was used for stable transformation of tobacco. Some of the transgenic plants obtained after selection showed enhanced GUS expression after exposure to some heavy metals. Maintenance of the plants for three generations, and the analysis of the response to treatments, suggest that these transgenic plants may be utilised as an affordable biomarker for monitoring heavy metal pollution.     

Ozonation as an advanced oxidant in treatment of bamboo industry wastewater

The present study employed ozonation process to treat the bamboo industry wastewater (BIWW). The impact of ozone dosage and initial organic concentration on color, COD and TOC removal rates were studied along with characterization of the major organics in raw and treated wastewater. The results suggested the ozone dosage of 3.15 g h⁻¹ (concentration 52.5 mg L⁻¹) was suitable for the treatment. After 25 min ozonation of 1 L raw wastewater, the color, COD and TOC removal efficiencies were 95%, 56% and 40%, respectively, with an influent COD concentration of 835 mg L⁻¹. The ratio of kg O₃ kg⁻¹ COD at 3.15 g h⁻¹ was 2.8 (<3), revealing that ozonation was a cost effective process for tertiary treatment of BIWW. Longer oxidization time was required to achieve similar results for raw wastewater with higher COD concentration. The chromatogram from gel permeation chromatography revealed that ozonation resulted in the breakdown of high molecular weight compounds into lower molecular weight components but could not completely mineralize the organic matter. The majority of these compounds were identified in both raw and ozonated samples via GC-MS analysis. In addition to ester derivatives as the main intermediates of ozonation, 1-chloroctadecane, methyl stearate, benzophenone and α-cyperone were identified as the by-products of ozonation.     

Metallothionein-like proteins in the freshwater oligochaete Limnodrilus udekemianus and their role as a homeostatic mechanism against cadmium toxicity

The purpose of this study was to determine if metallothioneins are present in the aquatic oligochaete Limnodrilus udekemianus and to determine the interplay between the presence of these proteins, cadmium (Cd) exposure, and Cd toxicity. The latter was geared specifically towards evaluating the role of metallothionein as a homeostatic mechanism against Cd toxicity. These issues are important for evaluating the usefulness of the quantification of metallothioneins as a biomonitoring tool. Worms in sediment were exposed to Cd under static conditions, with Cd initially added to the aqueous phase. Survival was monitored while respiration (as a measure of sublethal Cd effects) was determined immediately following exposure. Metallothioneins were separated from the cytosol by gel permeation high performance liquid chromatography (HPLC) while Cd levels were quantified in whole worms, cytosol and cytosolic fractions. Also, a Cd-saturation assay was used to determine the amounts of Cd bound to metallothionein and the total Cd-binding capacity of the metallothionein. Limnodrilus udekemianus has a metallothionein-like protein (an inducible cytosolic protein with an apparent molecular weight of approximately 15 kD that binds high levels of Cd and shows a red shift upon Cd binding). Sediment Cd levels above 60 microg/g were lethal to the worms (in 8-day exposures). Respiration rates at 13 and 41 microg/g Cd were not significantly different from controls, though cytosolic Cd levels were substantially increased in the 41 microg/g exposure. In this latter cytosol, Cd levels were significantly elevated in the low molecular weight pool (which includes metallothioneins) but not in the other pools, while the Cd-saturation assay also showed that worms in this group had significantly elevated levels of metallothionein-bound Cd. However, in all treatments the metallothionein was far from saturated by Cd. These observations indicate that no 'spill-over' of Cd was evident as lethal levels of Cd were approached. The overall cytosolic Cd distribution, and the degree of metallothionein saturation in Limnodrilus udekemianus thus do not appear to be good predictors of Cd toxicity in this species.     

Absorption of selenium by Lactuca sativa as affected by carboxymethylcellulose

Several organic compounds of high molecular weight present in soil interact with selenium and may act as active binding agents affecting its availability in soil, and, consequently, selenium uptake by plants. This study is aimed at investigating the effects of polysaccharides on selenium speciation in soil and on selenium absorption by Lactuca sativa L. plants. Three-week-old seedlings were transplanted into pots filled with soil, and sodium selenite at rates of 1.5 and 5mgSekg(-1) of soil, or sodium selenate at a rate of 1.5mgSekg(-1) of soil were applied. Carboxymethylcellulose (CMC) was added to the soil at rates of 0, 3 and 30mgkg(-1) of soil. After 48 and 110d from transplanting plants were harvested, separated into root and shoot, and fresh and dry matter weights were recorded. Total selenium was determined in both soil and plant samples. A sequential extraction was used to investigate the different Se oxidation states and assess the availability of Se in soil after the final harvesting. Both selenite and selenate were absorbed by roots, but plants amended with Se(VI+) showed higher selenium concentration than plants amended with Se(IV+). Selenite appears to be less mobile than selenate both in soil and plants. The addition of carboxymethylcellulose to soil decreased the amount of selenium absorbed by plants. CMC interacted with Se, making it less mobile as evidenced by the increase in the insoluble fractions. The insoluble Se forms in soil may represent environmental Se sinks potentially available for plants if the substrate is re-used for subsequent growth cycles and selenium species are mobilized as a result of biological and chemical processes.     

Responses of juvenile sea bass, Dicentrarchus labrax, exposed to acute concentrations of crude oil, as assessed by molecular and physiological biomarkers

In the present study, juvenile sea bass were exposed for 48 and 96 h to an Arabian light crude oil and their responses were assessed at the molecular and physiological levels. The aim of the study was therefore to assess (i) the short term effects of crude oil exposure by the measurement of several molecular biomarkers, (ii) the consequences of this short term exposure on fish health by using growth and condition indices measured after a decontamination period of 28 and 26 d in seawater. Hydrocarbon petroleum concentrations was monitored during the 96 h experiments and an increase of PAH concentrations were found in fish following both exposure times. An 7-ethoxyresorufin-O-deethylase (EROD) induction was observed after 48 h of exposure, while a significant decrease in the sea bass specific growth rate in length and for the RNA:DNA ratio was observed 28 d after that exposure ceased. The EROD induction doubled after the 96 h exposure, and a significant increase in GST activities was observed. A significant decrease in the specific growth rates, the otolith recent growth, the RNA:DNA ratio and the Fulton’s K condition index were then observed in sea bass 26 d after the 96 h exposure to mechanically dispersed crude oil compared to the control. The present study shows that growth and condition indices can prove useful in assessing fish health status following an oil spill. Their complementary analysis with sensitive molecular biomarkers as EROD could improve the determination of oil spill impact on fish populations.     

The assessment of electromigration as a new technique to study diffusion of radionuclides in clayey soils

For the performance assessment study of a geological disposal of High Level Waste (HLW) in clayey formations, migration studies are essential. For low permeability soils (clays), classical diffusion studies take a very long time. In order to reduce the experimental time, we propose an electrical field as driving force to accelerate the migration of ionic species. This paper reports the assessment of the electromigration technique as a powerful new and fast technique for migration studies. The apparent molecular diffusion coefficient can be derived by two independent methods using the migration parameters obtained from an electromigration experiment, namely the apparent dispersion coefficient and the apparent convection velocity. First, it can be calculated from the velocity of the migrating species by the Einstein relation. But, corrections are necessary for electroosmotic flow. The apparent electroosmotic mobility is experimentally determined as 2.2·10⁻⁹ m²/Vs. Second, it can be calculated from the relation between the apparent dispersion coefficient and the total apparent convection velocity. But it is necessary to know the dispersion length of the medium. The dispersion length for Boom Clay is experimentally determined as 8·10⁻⁵ m. Because of the serious reduction in time, it becomes possible to run series of experiments at different electrical fields to obtain averaged values for the apparent molecular diffusion coefficient according to the two methods. Experiments at different electrical fields have another advantage: the intercept of the linear relationship between the total apparent convection velocity and the apparent dispersion coefficient gives the apparent molecular diffusion coefficient. The apparent molecular diffusion coefficients obtained for ⁸⁵Sr, ¹³¹I and HTO are respectively 0.8·10⁻¹¹, 15·10⁻¹¹, and 24·10⁻¹¹ m²/s. These values are confirmed by pure diffusion experiments. The excellent agreement with the apparent molecular diffusion coefficients obtained by classical diffusion tests clearly demonstrates the feasibility of the electromigration technique for the determination of diffusion coefficients.     

IV. Recovery of Flue Gas Sulfur as Ammonium Phosphate

The present development in industry has greatly increased the consumption of fossil fuel all over the world. The sulfur present in these fuels on combustion impairs the atmosphere and has to be removed before or after combustion. Direct desulfurization is still in its initial stage of commercial application and is thought to be rather expensive. Most projects today are concerned with flue gas desulfurization and a few people have been successful in the pilot plant scale. Flue gas sulfur is usually recovered as sulfuric acid or ammonium sulfate. The Kiyoura-T.I.T. process employs a completely dry method to recover this sulfur as ammonium sulfate. However, the present trends in fertilizers show that there is a marked drop in the consumption of this type of fertilizer except for China and other Asian countries.

Experiments were carried out to produce a high grade phosphatic fertilizer with a larger field of application. The authors were successful in rendering the phosphate in phosphate rock water soluble by reacting it with the sulfate radical of the ammonium sulfate. Ammonium acid sulfate was used in the experiments and the phosphate radical was determined by a colorimeter utilizing the ammonium molybdate method.

The results showed a conversion and an extractability of 98%, when the molecular ratio of ammonium acid sulfate to the CaO in phosphate rock was in the vicinity of 1:1.4-1.5. The reaction time was 120-180 minutes.

The extracted liquid was crystallized and put through X ray diffractometer experiments which showed that most of the crystals were ammonium phosphate containing about 15% N and 39% P₂O₅ on a dry basis. Thus, it is evident that this could be effectively applied in a commercial scale plant, recovering the flue gas sulfur as ammonium phosphate. The Kiyoura-T.I.T. process can be utilized to recover the flue gas sulfur either as the sulfate or as the phosphate.     

Optimal descriptor as a translator of eclectic information into the prediction of membrane damage by means of various TiO2 nanoparticles

The increasing use of nanomaterials incorporated into consumer products leads to the need for developing approaches to establish “quantitative structure–activity relationships” (QSARs) for various nanomaterials. However, the molecular structure as rule is not available for nanomaterials at least in its classic meaning. An possible alternative of classic QSAR (based on the molecular structure) is the using of data on physicochemical features of TiO₂ nanoparticles. The damage to cellular membranes (units L⁻¹) by means of various TiO₂ nanoparticles is examined as the endpoint.     

Microbial phytotoxins as potential herbicides

Abstract

Microbes are sources of a diverse array of phytotoxic compounds. These compounds are generally structurally different from commercial herbicides, targeting different molecular sites of action within the plant. These novel structures and sites can be excellent leads for the discovery and development of safer synthetic herbicides. Microbial phytotoxins are often more environmentally benign than synthetic herbicides. Examples of phytotoxins from fungi (AAL‐toxin, cornexistin, cyperin, and tentoxin) with novel structures and sites of action are discussed. AAL‐toxin is toxic to a wide variety of weeds at very low dose rates. AAL‐toxin and many of its analogues kill plants by inhibiting a ceramide synthase‐like enzyme, causing rapid accumulation of free sphingoid bases that disrupt membranes. Cornexistin appears to be metabolically cnverted to an inhibitor of certain aspartate amino transferase isoenzymes. Its activity can be reversed by feeding aspartate and glutamate or with tricarboxylic acid cycle intermediates. Its activity is much like that of (aminooxy)acetate. Cyperin is a diphenylether phytotoxin that inhibits protoporphyrinogen oxidase, but does not kill plants by this mechanism. It appears to have other effects on porphyrin metabolism. Tentoxin is toxic by two mechanisms. It disrupts chloroplast development by inhibiting the processing of a nuclear‐coded plastid protein, and it also inhibits photophosphorylation by acting as an energy transfer inhibitor of coupling factor 1 ATPase. Other examples of phytotoxins from microbes with promise as herbicides will be mentioned.     

Chitosan/glyphosate formulation as a potential,environmental friendly herbicide with prolonged activity

Although there are many reports on the dangers posed by glyphosate, this herbicide is still one of the most popular and widely used total weed killers. Therefore, great effort should be made to minimize exposure to this herbicide and limit its losses into the environment. The aim of this study was to prepare a new formulation consisted of various molecular weight chitosans with glyphosate and their evaluation toward active substance release, phytotoxicity, and preliminary herbicidal efficiency. The phytotoxicity study of the obtained chitosan/glyphosate formulations was determined based on the Organisation for Economic Co-operation and Development 208 guideline. Among all tested formulations evaluated for phytotoxicity, that containing the highest molecular weight of chitosan was found to be the least toxic, showing simultaneously the most effective herbicidal activity against selected weeds. The release rate of glyphosate from the obtained formulations was dependent on the molecular weight and viscosity of chitosan.     

Validation of germination rate and root elongation as indicator to assess phytotoxicity with Cucumis sativus

Germination rate and root elongation, as a rapid phytotoxicity test method, possess several advantages, such as sensitivity, simplicity, low cost and suitability for unstable chemicals or samples. These advantages made them suitable for developing a large-scale phytotoxicity database and especially applicable for developing quantitative structure–activity relationship (QSAR) to study mechanisms of phytotoxicity. In this paper, the comparative inhibition of germination rate and root elongation of Cucumis sativus by selected halogen-substituted phenols and anilines were determined. The suitability of germination rate and root elongation as phytotoxicity endpoints was evaluated. Excellent reproducibility and stability of germination rate and root elongation in the control test, relatively greater sensitivity and similar dose–response relations for all tested compounds were observed. These results together with those of a 2-day test were used to demonstrate the suitability of this phytotoxicity test method. A QSAR was developed for the phytotoxicity mode of action of the tested compounds to C. sativus seeds. Models that combined the logarithm of 1-octanol/water partition coefficient (log K_ow) and the energy of the lowest unoccupied molecular orbital (E_lumo) were developed for both germination rate inhibition and root elongation inhibition. The results of these studies indicate that phytotoxicity of substituted phenols and anilines to C. sativus seeds could be explained by a polar narcosis mechanism. This paper will promote the application of germination rate and root elongation method and the development of large-scale phytotoxicity database, which will provide the fundamental data for QSAR and ecological risk assessment of organic pollutants.     

Insights into the structural and conformational requirements of polybrominated diphenyl ethers and metabolites as potential estrogens based on molecular docking

PBDEs and their metabolites are of concern due to their increasing concentrations in the environment and their toxic effects. Knowledge about the toxicological mechanisms of PBDEs and metabolites is urgently needed for further screening. The objective of the present study was to explore the structural and conformational requirements of PBDE compounds as human estrogen receptor alpha (hERα) agonists, and further screened out hERα agonists from PBDE compounds. Molecular docking and postdocking analysis were adopted to attain the aim. The obtained results revealed that PBDEs can be primarily screened for their estrogenicity using score values, hydrogen bonds interaction with amino acid residues Glu353 and/or Arg394 might be important for HO-PBDEs’ estrogenicity. For most MeO-PBDEs, hydrophobic interaction might be the key factor affecting their estrogenic activity. The current study suggested that molecular docking and postdocking analysis can serve as an efficient pre-screening technique for identifying potential estrogens.     

Chitosan/albumin/CaCO3 as mimics for membrane bioreactor fouling: genesis of structural mineralized-EPS-building blocks and cake layer compressibility

Membrane bioreactor biofouling is usually described as an extracellular matrix in which biopolymers, inorganic salts and active microbes co-exist. For that reason, biomineralization (BM) models can be useful to describe the spatial organization and environmental constraints within the referred scenario. BM arguments were utilized as background in order to (1) evaluate CaCO₃ influence on flux decline; pore blocking and cake layer properties (resistance, permeability and compressibility) in a wide range of Chitosan/Bovine serum albumin (BSA) mixtures during step-pressure runs and, (2) perform membrane autopsies in order to explore the genesis of mineralized extracellular building blocks (MEBB) during cake layer build up. Using low molecular weight chitosan (LC) and BSA, 2 L of 5 LC/BSA mixtures (0.25-1.85 ratio) were pumped to an external ultra filtration (UF) membrane (23.5 cm², hydrophobic, piezoelectric, 100 kDa as molecular weight cut-off). Eight different pressure steps (40 ± 7 to 540 ± 21 kPa) were applied. Each pressure step was held for 900 s. CaCO₃ was added to LC/BSA mixtures at 0.5, 1.5 and 3 mM in order to create MEBB during the filtration tests. Membrane autopsies were performed after the filtration tests using thermo gravimetric, scanning microscopy and specific membrane mass (mg cm⁻²) analyses. Biopolymer-CaCO₃ step-pressure filtration created compressible cake layers (with inner voids). The formation of an internal skeleton of MEBB may contribute to irreversible fouling consolidation. A hypothesis for MEBB genesis and development was set forth.     

Molecular markers, essential oils and diagnostic parameters as indicators for assessing the origin and constitution of organic matter in atmospheric aerosols

Atmospheric particulate matter was collected at two sites: an Abies boressi forest in central Greece and in Giesta, a coastal-rural site in the centre of Portugal. The extractable organic material consisted primarily of aliphatic hydrocarbons, acids, alcohols, and ketones, with a predominance of molecular weights >C20, derived from vascular plant waxes. Biomarkers for vegetation sources such as phytosterols, triterpenic compounds and essential oils were also detected. Microbial components (>C20), pyrogenic aromatic hydrocarbons and petroleum residues, including hopanes, steranes and cyclic and branched hydrocarbons, were present in the various aerosol extracts. In the apportionment of the various organic fractions to sources, vegetation waxes dominated, contributing to 50–60% of the solvent-extractable material in the aerosols. Petroleum residues and microbial components comprise 25–30% and 15–25% of the organic matter, respectively.