Development of Gas-phase Pre-separation Tools for Higher Sensitivity in the Molecular Characterization of Biodiesel Mixtures

The analysis of complex mixtures without pre-fractionation is analytically challenged by the high number of chemical components and their wide concentration range. In addition, many chemical species are difficult to ionize and charge competition may occur prior to mass analyses, thus limiting the detection capabilities of any analytical instrument. In the present work, we show the advantages of gas-phase separation prior to high resolution mass spectrometry analysis. In particular, two biodiesel fuel standards (soy and animal based) were analyzed using a novel analytical method featuring gas chromatographic separation prior to atmospheric pressure laser ionization (APLI). Results showed that gas- phase separation allows for 57 % and 39 % increases in the number of compounds detected from the soy-based and animal-based samples, respectively, when compared with direct infusion. Results also suggest that the molecular ion signal increase is achieved through the reduction of the ion suppression within the plume of the spray- based atmospheric pressure ionization sources (also valid for ESI, APCI, APPI sources). Accurate mass measurements (? \u3c 0.5 ppm) via Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) enabled unambiguous identification of over 2,000 molecular ions per sample in the m/z=150-550 range. Inspection of the Kendrick and van Krevelen plots revealed that ion suppression when using APLI appears to be mostly concentration dependent regardless of the chemical class; that is, it does not depend on aromaticity, polarizability, or mass range

Online solid phase extraction liquid chromatography tandem mass spectrometry (SPE-LC-MS/MS) method for the determination of sucralose in reclaimed and drinking waters and its photo degradation in natural waters from South Florida

Background Sucralose has gained popularity as a low calorie artificial sweetener worldwide. Due to its high stability and persistence, sucralose has shown widespread occurrence in environmental waters, at concentrations that could reach up to several μg/L. Previous studies have used time consuming sample preparation methods (offline solid phase extraction/derivatization) or methods with rather high detection limits (direct injection) for sucralose analysis. This study described a faster and sensitive analytical method for the determination of sucralose in environmental samples. Results An online SPE-LC–MS/MS method was developed, being capable to quantify sucralose in 12 minutes using only 10 mL of sample, with method detection limits (MDLs) of 4.5 ng/L, 8.5 ng/L and 45 ng/L for deionized water, drinking and reclaimed waters (1:10 diluted with deionized water), respectively. Sucralose was detected in 82% of the reclaimed water samples at concentrations reaching up to 18 μg/L. The monthly average for a period of one year was 9.1 ± 2.9 μg/L. The calculated mass loads per capita of sucralose discharged through WWTP effluents based on the concentrations detected in wastewaters in the U. S. is 5.0 mg/day/person. As expected, the concentrations observed in drinking water were much lower but still relevant reaching as high as 465 ng/L. In order to evaluate the stability of sucralose, photodegradation experiments were performed in natural waters. Significant photodegradation of sucralose was observed only in freshwater at 254 nm. Minimal degradation (\u3c20%) was observed for all matrices under more natural conditions (350 nm or solar simulator). The only photolysis product of sucralose identified by high resolution mass spectrometry was a de-chlorinated molecule at m/z 362.0535, with molecular formula C12H20Cl2O8. Conclusions Online SPE LC-APCI/MS/MS developed in the study was applied to more than 100 environmental samples. Sucralose was frequently detected (\u3e80%) indicating that the conventional treatment process employed in the sewage treatment plants is not efficient for its removal. Detection of sucralose in drinking waters suggests potential contamination of surface and ground waters sources with anthropogenic wastewater streams. Its high resistance to photodegradation, minimal sorption and high solubility indicate that sucralose could be a good tracer of anthropogenic wastewater intrusion into the environment

Assessment of natural resource conditions in and adjacent to Biscayne National Park. Natural Resource Report NPS/BISC/NRR—2012/598

This report is an assessment of the conditions of natural resources in Biscayne National Park (BNP) based on the compilation, review and evaluation of existing information on the Park’s natural resources. This review evaluates threats and stressors, and is intended to improve understanding of BNP resources to help guide Park management to address the identified threats, which are supported by enhanced data collection, research and assessment efforts. The report is focused on broad resource components, namely terrestrial resources and aquatic systems including: wetlands, canals, bay waters, marine/reef areas and ground waters. Biotic and abiotic resource components are considered in the review

Potential Impacts of PCBs on Sediment Microbiomes in a Tropical Marine Environment

Within the tropical marine study site of Guánica Bay, Puerto Rico, polychlorinated biphenyls (PCBs) are subjected to coastal and oceanic currents coupled with marine microbial and geochemical processes. To evaluate these processes a hydrodynamic model was developed to simulate the transport of PCBs within nearshore and offshore marine areas of Guánica Bay. Material transport and circulation information from the model were matched with measurements from samples collected from within the bay. These samples, consisting of both intertidal and submerged sediments, were analyzed for physical characteristics (organic carbon, grain size, and mineralogy), microbial characteristics (target bacteria levels and microbial community analyses), presence of PCBs, and PCB-degrading enzymes. Results show that the bay geometry and bathymetry limit the mixing of the extremely high levels of PCBs observed in the eastern portion of the bay. Bay bottom sediments showed the highest levels of PCBs and these sediments were characterized by high organic carbon content and finer grain size. Detectable levels of PCBs were also observed within sediments found along the shore. Microbes from the bay bottom sediments showed a greater relative abundance of microbes from the Chloroflexi, phylum with close phylogenetic associations with known anaerobic PCB-degrading organisms. Based on quantitative PCR measurement of the biphenyl dioxygenase gene, the intertidal sediments showed the greatest potential for aerobic PCB degradation. These results elucidate particular mechanisms of PCB’s fate and transport in coastal, tropical marine environments

Oil Hydrocarbon Degradation by Caspian Sea Microbial Communities

The Caspian Sea, which is the largest landlocked body of water on the planet, receives substantial annual hydrocarbon input from anthropogenic sources (e.g., industry, agriculture, oil exploration, and extraction) and natural sources (e.g., mud volcanoes and oil seeps). The Caspian Sea also receives substantial amounts of runoff from agricultural and municipal sources, containing nutrients that have caused eutrophication and subsequent hypoxia in the deep, cold waters. The effect of decreasing oxygen saturation and cold temperatures on oil hydrocarbon biodegradation by a microbial community is not well characterized. The purpose of this study was to investigate the effect of oxic and anoxic conditions on oil hydrocarbon biodegradation at cold temperatures by microbial communities derived from the Caspian Sea. Water samples were collected from the Caspian Sea for study in experimental microcosms. Major taxonomic orders observed in the ambient water samples included Flavobacteriales, Actinomycetales, and Oceanospirillales. Microcosms were inoculated with microbial communities from the deepest waters and amended with oil hydrocarbons for 17 days. Hydrocarbon degradation and shifts in microbial community structure were measured. Surprisingly, oil hydrocarbon biodegradation under anoxic conditions exceeded that under oxic conditions; this was particularly evident in the degradation of aromatic hydrocarbons. Important microbial taxa associated with the anoxic microcosms included known oil degraders such as Oceanospirillaceae. This study provides knowledge about the ambient community structure of the Caspian Sea, which serves as an important reference point for future studies. Furthermore, this may be the first report in which anaerobic biodegradation of oil hydrocarbons exceeds aerobic biodegradation

First issue ENMM

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Determinazione delle fibre di carbonio pre-impregnate con resine di vario tipo attraverso monitoraggio ambientale e loro misura nel condensato dell'aria esalata per la valutazione del rischio dei lavoratori esposti.

Le fibre di carbonio sono fibre organiche artificiali costituite da polimeri di carbonio strutturati in forma grafitica, generalmente rinforzate con resine epossidiche o di altro tipo per la realizzazione di materiali compositi. L’obiettivo della ricerca è stato studiare mediante monitoraggio ambientale e biologico l’esposizione occupazionale a fibre di carbonio pre-impregnate con resine di vario tipo nei lavoratori di un impianto di produzione di componenti di aeromobili, per la valutazione del rischio

Increasing Polyaromatic Hydrocarbon (PAH) Molecular Coverage during Fossil Oil Analysis by Combining Gas Chromatography and Atmospheric-Pressure Laser Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS)

Thousands of chemically distinct compounds are encountered in fossil oil samples that require rapid screening and accurate identification. In the present paper, we show for the first time, the advantages of gas chromatography (GC) separation in combination with atmospheric-pressure laser ionization (APLI) and ultrahigh-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) for the screening of polyaromatic hydrocarbons (PAHs) in fossil oils. In particular, reference standards of organics in shale oil, petroleum crude oil, and heavy sweet crude oil were characterized by GC-APLI-FT-ICR MS and APLI-FT-ICR MS. Results showed that, while APLI increases the ionization efficiency of PAHs, when compared to other ionization sources, the complexity of the fossil oils reduces the probability of ionizing lower-concentration compounds during direct infusion. When gas chromatography precedes APLI-FT-ICR MS, an increase (more than 2-fold) in the ionization efficiency and an increase in the signal-to-noise ratio of lower-concentration fractions are observed, giving better molecular coverage in the <i>m</i>/<i>z</i> 100–450 range. That is, the use of GC prior to APLI-FT-ICR MS resulted in higher molecular coverage, higher sensitivity, and the ability to separate and characterize molecular isomers, while maintaining the ultrahigh resolution and mass accuracy of the FT-ICR MS separation

Ambient Iron-Mediated Aeration (IMA) for Water Reuse

Global water shortages caused by rapidly expanding population, escalating water consumption, and dwindling water reserves have rendered water reuse a strategically significant approach to meet current and future water demand. This study is the first to our knowledge to evaluate the technical feasibility of iron-mediated aeration (IMA), an innovative, potentially economical, holistic, oxidizing co-precipitation process operating at room temperature, atmospheric pressure, and neutral pH, for water reuse. In the IMA process, dissolved oxygen (O2) was continuously activated by zero-valent iron (Fe0) to produce reactive oxygen species (ROS) at ambient pH, temperature, and pressure. Concurrently, iron sludge was generated as a result of iron corrosion. Bench-scale tests were conducted to study the performance of IMA for treatment of secondary effluent, natural surface water, and simulated contaminated water. The following removal efficiencies were achieved: 82.2% glyoxylic acid, ∼100% formaldehyde as an oxidation product of glyoxylic acid, 94% of Ca2+ and associated alkalinity, 44% of chemical oxygen demand (COD), 26% of electrical conductivity (EC), 98% of di-n-butyl phthalate (DBP), 80% of 17β-estradiol (E2), 45% of total nitrogen (TN), 96% of total phosphorus (TP), 99.8% of total Cr, \u3e90% of total Ni, 99% of color, 3.2 log removal of total coliform, and 2.4 log removal of E. Coli. Removal was attributed principally to chemical oxidation, precipitation, co-precipitation, coagulation, adsorption, and air stripping concurrently occurring during the IMA treatment. Results suggest that IMA is a promising treatment technology for water reuse