Chemical characterization of volatile organic compounds emitted by animal manure.

Animal manure is considered a valuable organic fertilizer due to its important nutrient content enhancing soil fertility and plant growth in agriculture. Besides its beneficial role as fertilizer, animal manure represents a significant source of volatile organic compounds (VOCs), playing a significant role in atmospheric chemistry. Understanding the composition of VOCs Understanding VOCs from animal manure is crucial for assessing their environmental impact, as they can cause air pollution, odors, and harm to human health and ecosystems. Laboratory studies enhance field measurements by providing a precise inventory of manure emissions, addressing gaps in existing literature. Both approaches complement each other in advancing our understanding of manure emissions. In this context, we conducted an experimental study involving various animal manures (cow, horse, sheep, and goat) taken from a farm in Grignon (near Paris, France). We employed atmospheric simulation chambers within a controlled laboratory environment. The analysis of VOCs involved the combination of Proton Transfer Reaction-Quadrupole ion guide-Time-of-Flight Mass Spectrometry (PTR-QiTOF-MS) and Thermal Desorption-Gas Chromatography-Mass Spectrometry (TD-GC-MS). Using PTR-QiTOF-MS, 368 compounds were detected and quantified within the manure samples. The complementary analysis by TD-GC-MS enhanced our identification of VOCs. Our findings revealed various chemical groups of VOCs, including oxygenated compounds (e.g., ethanol, cresol, acetaldehyde, etc.), nitrogenated compounds (ammonia, trimethylamine, etc.), sulfur compounds (methanethiol, dimethyl sulfide, etc.), aromatic compounds (phenols and indoles), terpenes (isoprene, D-limonene, etc.) and halogenated compounds. Cow manure exhibited the highest VOC emission fluxes, followed by goat, sheep, and horse manures. Notably, oxygenated VOCs were dominant contributors to total VOC emission fluxes in all samples. Statistical analysis highlighted the distinct nature of cow manure emissions, characterized by oxygenated compounds and nitrogenated compounds. In addition, goat manure was isolated from the other samples with high emissions of compounds having both oxygen and nitrogen atoms in their molecular formulas (e.g., CH3NO2). The experimental dataset obtained in this study provides an inventory reference for both VOCs and their emission fluxes in animal manures. Furthermore, it highlights odorant compounds and VOCs that serve as atmospheric aerosol precursor. Future studies can explore the effectiveness of various manure treatment methods to promote sustainable agriculture practices.

Chemical identification and quantification of volatile organic compounds emitted by sewage sludge.

The recycling of organic waste products (e.g. sewage sludge, SS) is currently being promoted as a substitute for mineral fertilizers for agricultural lands. The spreading of SS allows the recycling of the nutrients and organic matter it contains. SS contains various pollutants such as volatile organic compounds (VOCs) that adversely affect the ecosystem and human health through ozone production and serve as critical precursors of atmospheric secondary organic aerosols. There are very few studies quantifying the gaseous compounds emitted from SS, and those studies primarily address their odorant properties for identifying suitable odour abatement techniques. There is an urgent need for more comprehensive quantitative information on VOCs emitted from SS as aerosol precursors. In this context, an experimental study was performed on SS samples taken from a wastewater treatment plant located in France. Undigested SS (UDSS), digested SS (DSS) and SS with 30% and 60% dryness were collected from different stages of treatment sequence and analyzed using atmospheric simulation chambers coupled to proton-transfer-reaction quadrupole ion-guide time-of-flight mass spectrometer. Our study revealed that SS samples emitted a large spectrum of VOCs. 380 compounds were detected, quantified and classified into different chemical groups. The VOC emissions increased with the increase in the dryness of the sample; the highest being in SS 60%, followed by SS 30%, UDSS and DSS. OVOCs were dominant in SS 60%. The statistical analysis showed that the anaerobic digestion and the dewatering to 60% of dryness decreased the emissions of sulphuric compounds. Aromatic compounds and indoles (e.g. skatole) were emitted significantly from the UDSS. Some of these VOCs can serve as precursor gases for atmospheric aerosol formation. The experimental dataset obtained in this study provides an accurate inventory reference for the VOC emissions from SS samples and shows the impacts of the treatment on emission characteristics of VOCs.

Fine particles sampled at an urban background site and an industrialized coastal site in Northern France - Part 1: Seasonal variations and chemical characterization.

The chemical composition of particulate matter sampled at two French Northern sites (Douai, DO - urban background; Grande-Synthe, GS - industrialized coastal site) was investigated during two summer and winter field campaigns at each site. Measurements of the major chemical species (organic, sulfate, nitrate, ammonium, chloride) in the non-refractory submicron aerosols (NR-PM1) were carried out by a High Resolution Time-of-Flight Aerosol Mass Spectrometer. Black Carbon in PM2.5 was monitored using an Aethalometer, while the OC and EC fractions and some targeted chemical organic families (polycyclic aromatic hydrocarbons, PAHs; dicarboxylic acids, DCAs) were quantified by the simultaneous collection of PM2.5 on filters followed by offline analyses. The seasonal trends and winter-to-summer (W/S) concentration ratios are discussed in this paper. Results indicate that the total average mass concentrations of PM2.5 varied between 20.5µgm-3 and 32.6µgm-3 in DO and between 10.6µgm-3 and 29.9µgm-3 in GS during summer and winter, respectively. Similar concentration patterns were found for PAHs and Organic Carbon (OC, representing ~80% of the total carbon) with highest concentrations in winter at the urban site. DCA concentrations showed less seasonal variations, although the highest value also appeared during winter. Total NR-PM1 presented concentrations in summer lower by a factor of 4 (for DO) and 10 (for GS) than those observed in winter. Organics and nitrates dominated the NR-PM1 in DO for both seasons and during winter in GS while sulfates and nitrates were the most dominant species in summer in GS. Average chloride concentrations were slightly more important in GS than those in DO related to its use in industrial processes and no significant seasonal trend was observed. The size-resolved chemical composition showed that aerosols sampled in DO in winter are more aged than those collected in GS where fresh emissions of sulfate from the industrial sector were observed.

Influence of stearic acid coating of the NaCl surface on the reactivity with NO2 under humidity.

In the atmosphere, sea salt aerosols, containing mainly NaCl, can accumulate fatty acids and undergo heterogeneous chemistry with atmospheric nitrogen oxides. The effect of stearic acid (SA) coating on the reactivity of the NaCl(100) surface with NO2 under humidity was studied by atomic force microscopy (AFM), Raman mapping and time-of-flight secondary ion mass spectrometry (ToF-SIMS) to highlight processes occurring on NaCl surfaces. The vapor-deposition of SA on the NaCl surface generates heterogeneous coating with discontinuous monolayer islands. The SA molecules with all-trans conformation stick to the NaCl surface through -CO2H groups and are organized in parallel between them and nearly perpendicularly to the surface. The SA coating does not prevent the NaNO3 particle formation when the sample is exposed to NO2 under low humidity conditions. The initial abilities of the NaCl surface coated with SA to pick up NO2 from the gas phase are correlated with the fraction of bare NaCl area evidencing the spatially heterogeneous reactivity of the surface. The role of H2O in the NO2 uptake and the catalytic conversion of NaCl to NaNO3 is shown. Under humidity (RH = 50%), the H2O uptake by NaNO3 particles on the coated-NaCl surface is significantly more important than that adsorbed under analogous conditions without the presence of NaNO3 particles. This unusual water absorption initiates transitions (i) from solid NaNO3 particles to NaNO3 aqueous solution and (ii) from the SA monolayer with well-ordered all trans alkyl chains to the SA gel with completely disordered conformation. This mixed SA/NaNO3 layer on the particle surface may have significant consequences on the hygroscopic properties and reactivity of the sea salt aerosols in the atmosphere.

The chiral molecule CHClFI: first determination of its molecular parameters by Fourier transform microwave and millimeter-wave spectroscopies supplemented by ab initio calculations.

The rotational spectrum of chlorofluoroiodomethane (CHClFI) has been investigated. Because its rotational spectrum is extremely crowded, extensive ab initio calculations were first performed in order to predict the molecular parameters. The low J transitions were measured using a pulsed-molecular-beam Fourier transform spectrometer, and the millimeter-wave spectrum was measured to determine accurate centrifugal distortion constants. Because of the high resolution of the experimental techniques, the analysis yielded accurate rotational constants, centrifugal distortion corrections, and the complete quadrupole coupling tensors for the iodine and chlorine nuclei, as well as the contribution of iodine to the spin-rotation interaction. These molecular parameters were determined for the two isotopologs CH35ClFI and CH37ClFI. They reproduce the observed transitions within the experimental accuracy. Moreover, the ab initio calculations have provided a precise equilibrium molecular structure. Furthermore, the ab initio molecular parameters are found in good agreement with the corresponding experimental values.

Characterization of human mucin gene MUC4 promoter: importance of growth factors and proinflammatory cytokines for its regulation in pancreatic cancer cells.

The human mucin gene MUC4 encodes a large transmembrane mucin that is thought to play important roles in tumor cell biology and that is overexpressed in human pancreatic carcinomas. In this report, we describe the structure and functional activity of the 5'-flanking region, including 1.0 kilobase of the promoter. The long 5'-untranslated region (2.7 kilobases) is characterized by a high content of GC in its 3'-end. The first TATA box was located at -2672/-2668. Multiple transcription start sites and a high density of putative binding sites for Sp1 (GC and CACCC boxes), AP-1/-2/-4, cAMP-responsive element-binding protein, GATA, GR, and STAT transcription factors were found within the 5'-flanking region. Transcriptional activity of the promoter was assessed using pGL3-luciferase deletion mutants in two MUC4-expressing (CAPAN-1 and CAPAN-2) and one nonexpressing (PANC-1) pancreatic cancer cell line. Two highly active fragments (-219/-1 and -2781/-2572) that drive MUC4 transcription in CAPAN-1 and CAPAN-2 cells were identified. Gel retardation assays indicated that Sp1 and Sp3 bind to cognate cis-elements found in the 5'-flanking region and that Sp1 transactivates, whereas Sp3 inhibits the GC-rich region (-464/-1) in CAPAN-2 cells. Activation of protein kinase C with phorbol ester and treatment of cells with epidermal growth factor and transforming growth factor-alpha resulted in up-regulation of the promoter. Tumor necrosis factor-alpha and interferon (IFN)-gamma inflammatory cytokines had no or mild effect on MUC4 transcriptional activity when used alone. However, a very strong synergistic effect (10-12-fold activation) between IFN-gamma and tumor necrosis factor-alpha or IFN-gamma and transforming growth factor-alpha was obtained in CAPAN-2 cells. Altogether these results demonstrate that the 5'-flanking region of MUC4 contains epithelial cell-specific, positive, and negative regulatory cis-elements, that Sp1/Sp3 are important regulators of MUC4 basal expression, and that its regulation in pancreatic cancer cells involves complex interplay between several signaling pathways.

Microwave Spectrum of 1-Cyano-3-fluoro-but-1-ene.

The rotational spectrum of the 1-cyano-3-fluoro-but-1-ene has been recorded with a pulsed-nozzle microwave Fourier transform spectrometer over the range 6-20 GHz. The frequencies were fitted to the Hamiltonian of Watson (A-reduction, I(r) representation). The resulting rotational constants are A = 7493.404(1) MHz, B = 1211.9831(2) MHz, and C = 1096.0908(1) MHz. By comparing the experimental rotational constants with those obtained by ab initio calculations, we found without ambiguity that the stable conformation for the molecule is the one with the fluorine atom lying in the C&bond;CCN plane (CF-eclipsed conformer). Copyright 2000 Academic Press.

Rotational Spectrum of Vinylarsine.

The rotational spectrum of vinylarsine in the ground state has been studied in the range 7-320 GHz. The spectra of a syn conformer and a gauche conformer have been unambiguously assigned on the basis of the existence of a b-type or a c-type spectrum. Rotational constants, quartic, and some sextic centrifugal distortion constants were derived. For the syn form, measurements of low J aR0,1 transitions in a pulsed-nozzle Fourier transform microwave spectrometer (FTMWS) enabled the determination of the diagonal elements of the quadrupole tensor, as well as two spin-rotation constants. Ab initio calculations performed at the MP2 level using the 6-311++G(3df, 3pd) basis set reproduced experimental rotational constants within 0.2%. Copyright 1998 Academic Press.

Human mucin gene MUC4: organization of its 5'-region and polymorphism of its central tandem repeat array.

In a previous study we isolated a partial cDNA with a tandem repeat of 48 bp, which allowed us to map a novel human mucin gene named MUC4 to chromosome 3q29. Here we report the organization and sequence of the 5'-region and its junction with the tandem repeat array of MUC4. Analysis of three overlapping genomic clones allowed us to obtain a partial restriction map of MUC4 and to locate the complete 48 bp tandem repeat domain on a PstI/EcoRI genomic fragment that exhibits a very large variation in number of tandem repeats (7-19 kb). cDNA clonal extension allowed us to obtain the entire 5' coding region of MUC4. Exon 1 consists of a 5' untranslated region and an 82 bp fragment encoding the signal peptide. This latter shows a high degree of similarity to the signal peptide of another apomucin, ASGP-1. Exon 2 is extremely large and contains a unique sequence that is followed by the whole tandem repeat domain. It encodes only one cysteine residue, making MUC4 different from mucin genes belonging to the 11p15.5 family. Moreover, an intron downstream from the tandem repeat array consists mainly of a 15 bp tandem repeat that exhibits a polymorphism in having a variable number of tandem repeats.

Evidence for different human tracheobronchial mucin peptides deduced from nucleotide cDNA sequences.

Highly glycosylated regions or glycopeptides were obtained by proteolysis of human tracheobronchial mucins. They were chemically deglycosylated and the resulting products were used to raise a rabbit antiserum. This antiserum specifically recognized the superanuclear region of respiratory and colonic goblet cells as areas around and below the nucleus of mucin-secreting cells in tracheobronchial mucous glands. A lambda gt11 cDNA library constructed from human tracheobronchial mucosa was screened with this antiserum. Ten positive clones were obtained from screening half of the library (about 10(6) recombinants). The antibodies were purified by absorption to each positive clone; some purified antibodies were specific for goblet cells and others recognized both goblet and mucous cells, indicating that there is differential cellular expression of mucin peptides. The total or partial amino acid sequences deduced from these cDNA clones could be classified into three groups. The first group contained repetitive sequences of eight amino acid residues, almost perfectly identical, and in different arrangements. The second type exhibited homology at their amino and carboxy-terminal ends. The last group had no distinctive feature except for a high content of hydroxy amino acids typical of mucins. Five different clones could correspond to the carboxy-terminal end of tracheobronchial apomucins. These results indicate that human tracheobronchial apomucins consist of a family of different proteins.

[Bronchial secretions: biochemical study. Physiopathological aspects]. / Les sécrétions bronchiques: étude biochimique. Aspects physio-pathologiques.

Among the chief constituents of bronchial secretions, serum or mucus proteins and mucins are the parameters enabling definition of the functional state of the tracheo-bronchial mucosa. The use of bronchial detergents in normal subjects or subjects with moderate secretions leads to the study of physiological sputum or to definition of the evolution of chronic bronchitis. Results of immunoglobulins G and A dosages, values of IgA 7S/IgA 11S and of IgA/serum albumin ratio are reported. In the same way, the equilibrium of secretion of mucins estimated by the percentage of the different classes of mucins separated according to their acidity degree is an evaluation element of the evolution degree of chronic bronchitis. The studies of correlation between rheological properties and chemical structure of bronchial secretions are reported. They postulate an original concept on the use of mucolytics.