Thermal stability of sewage sludge pyrolysis oil

The stability of the oil phase obtained from intermediate pyrolysis process was used for this investigation. The analysis was based on standard methods of determining kinematic viscosity, gas - chromatography / mass - spectrometry for compositional changes, FT-IR for functional group, Karl Fischer titration for water content and bomb calorimeter for higher heaating values. The methods were used to determine changes that occurred during ageing. The temperatures used for thermal testing were 60 °C and 80 °C for the periods of 72 and 168 h. Methanol and biodiesel were used as solvents for the analysis. The bio-oil samples contained 10 % methanol, 10 % Biodiesel, 20 % Biodiesel and unstabilised pyrolysis oil. The tests carried out at 80 °C showed drastic changes compared to those at 60 °C. The bio-oil samples containing 20 % biodiesel proved to be more stable than those with 10 % methanol. The unstabilised pyrolysis oil showed the greatest changes in viscosity, composition change and highest increase in water content. The measurement of kinematic viscosity and gas chromatograph mass spectrometry were found to be more reliable for predicting the ageing process.

Source/receptor reconciliation of ambient organic fine particulate matter in Palm Beach County

Airborne particulate matter (PM) is of environmental concern not only in urban but also rural areas that are easily inhalable and have been considered responsible, together with gaseous pollutants, for possible health effects. The objectives of this research study is to generate an extensive data set for ambient PM collected at Belle Glade and Delray Beach that ultimately was used together with published source profiles to predict the contributions of major sources to the overall airborne particle burden in Belle Glade and Delray Beach. ^ The size segregated particle sampling was conducted for one entire year. The samples collected during the months of January and May were further subjected to chemical analysis for organic compounds by Gas Chromatography-Mass Spectrometry. Additional, PM10 sampling was conducted simultaneously with size segregated particle sampling during January and May to analyze for trace elements using Instrumental Neutron Activation Analysis technique. Elements and organic marker compounds were used in Chemical Mass Balance modeling to determine the major source contribution to the ambient fine particle matter burden. ^ Size segregated particle distribution results show bimodal in both sampling sites. Sugarcane pre-harvest burning in the rural site elevated PM10 concentration by about 30% during the sugarcane harvest season compared to sugarcane growing season. Sea salt particles and Saharan dust particles accounted for the external sources. ^ The results of trace element analysis show that Al, Ca, Cs, Eu, Lu, Nd, Sc, Sm, Th, and Yb are more abundant at the rural sampling site. The trace elements Ba, Br, Ce, Cl, Cr, Fe, Gd, Hf, Na, Sb, Ta, V, and W show high abundance at the urban site due to anthropogenic activities except for Na and Cl, which are from sea salt spray. On the other hand, size segregated trace organic compounds measurements show that organic compounds mainly from combustion process were accumulated in PM0.95. ^ In conclusion, major particle sources were determined by the CMB8.2 software as follows: road dust, sugarcane leaf burning, diesel-powered and gasoline powered vehicle exhaust, leaf surface abrasion particles, and a very small fraction of meat cooking. ^

Chemical characteristics of dissolved organic matter in an oligotrophic subtropical wetland/estuarine ecosystem

Fluorescence properties of whole water samples and molecular characteristics of ultrafiltrated dissolved organic matter (UDOM > 1,000 D) such as lignin phenol and neutral sugar compositions and 13C nuclear magnetic resonance (NMR) spectra were determined along a freshwater to marine gradient in Everglades National Park. Furthermore, UDOM samples were categorized by hierarchical cluster analysis based on their pyrolysis gas chromatography/mass spectrometry products. Fluorescence properties suggest that autochthonous DOM leached/exuded from biomass is quantitatively important in this system. 13C NMR spectra showed that UDOM from the oligotrophic Taylor Slough (TS) and Florida Bay (FB) ecosystems has low aromatic C (13% ± 3% for TS; 2% ± 2% for FB) and very high O-alkyl C (54% ± 4% for TS; 75% ± 4% for FB) concentrations. High O-alkyl C concentrations in FB suggest seagrass/phytoplankton communities as dominant sources of UDOM. The amount of neutral sugars was not appreciably different between the TS and FB sites (115 ± 12 mg C g C-1 UDOM) but their concentrations suggest a low level of diagenesis and high production rates of this material in this oligotrophic environment. Total yield of lignin phenols (vanillyl + syringyl phenols) in TS was low (0.20–0.39 mg 100 mg C-1 UDOM) compared with other riverine environments and even lower in FB (0.04–0.07 mg 100 mg C-1 UDOM) and could be a result of photodegradation and/or dilution by other utochthonous DOM. The high O-alkyl and low aromatic nature of this UDOM suggests significant biogenic inputs (as compared with soils) and limited bioavailability in this ecosystem.

Determination of signature volatile odor chemicals emanating from novel biological specimens by non-invasive analytical techniques for the potential use in forensic identifications

Human scent, or the volatile organic compounds (VOCs) produced by an individual, has been recognized as a biometric measurement because of the distinct variations in both the presence and abundance of these VOCs between individuals. In forensic science, human scent has been used as a form of associative evidence by linking a suspect to a scene/object through the use of human scent discriminating canines. The scent most often collected and used with these specially trained canines is from the hands because a majority of the evidence collected is likely to have been handled by the suspect. However, the scents from other biological specimens, especially those that are likely to be present at scenes of violent crimes, have yet to be explored. Hair, fingernails and saliva are examples of these types of specimens. ^ In this work, a headspace solid phase microextraction gas chromatography-mass spectrometry (HS-SPME-GC-MS) technique was used for the identification of VOCs from hand odor, hair, fingernails and saliva. Sixty individuals were sampled and the profiles of the extracted VOCs were evaluated to assess whether they could be used for distinguishing individuals. Preliminary analysis of the biological specimens collected from an individual (intra-subject) showed that, though these materials have some VOCs in common, their overall chemical profile is different for each specimen type. Pair-wise comparisons, using Spearman Rank correlations, were made between the chemical profiles obtained from each subject, per a specimen type. Greater than 98.8% of the collected samples were distinguished from the subjects for all of the specimen types, demonstrating that these specimens can be used for distinguishing individuals. ^ Additionally, field trials were performed to determine the utility of these specimens as scent sources for human scent discriminating canines. Three trials were conducted to evaluate hair, fingernails and saliva in comparison to hand odor, which was considered the standard source of human odor. It was revealed that canines perform similarly to these alternative human scent sources as they do to hand odor implying that, though there are differences in the chemical profiles released by these specimens, they can still be used for the discrimination of individuals by trained canines.^

Assessment of the occurrence and potential risks of pharmaceuticals and their metabolites in fish and water using liquid chromatography mass spectrometry

A comprehensive method for the analysis of 11 target pharmaceuticals representing multiple therapeutic classes was developed for biological tissues (fish) and water. Water samples were extracted using solid phase extraction (SPE), while fish tissue homogenates were extracted using accelerated solvent extraction (ASE) followed by mixed-mode cation exchange SPE cleanup and analyzed by liquid chromatography tandem mass spectrometry (LC-MS/MS). Among the 11 target pharmaceuticals analyzed, trimethoprim, caffeine, sulfamethoxazole, diphenhydramine, diltiazem, carbamazepine, erythromycin and fluoxetine were consistently detected in reclaimed water. On the other hand, caffeine, diphenhydramine and carbamazepine were consistently detected in fish and surface water samples. In order to understand the uptake and depuration of pharmaceuticals as well as bioconcentration factors (BCFs) under the worst-case conditions, mosquito fish were exposed to reclaimed water under static-renewal for 7 days, followed by a 14-day depuration phase in clean water. Characterization of the exposure media revealed the presence of 26 pharmaceuticals while 5 pharmaceuticals including caffeine, diphenhydramine, diltiazem, carbamazepine, and ibuprofen were present in the organisms as early as 5 h from the start of the exposure. Liquid chromatography ultra-high resolution Orbitrap mass spectrometry was explored as a tool to identify and quantify phase II pharmaceutical metabolites in reclaimed water. The resulting data confirmed the presence of acetyl-sulfamethoxazole and sulfamethoxazole glucuronide in reclaimed water. To my knowledge, this is the first known report of sulfamethoxazole glucuronide surviving intact through wastewater treatment plants and occurring in environmental water samples. Finally, five bioaccumulative pharmaceuticals including caffeine, carbamazepine, diltiazem, diphenhydramine and ibuprofen detected in reclaimed water were investigated regarding the acute and chronic risks to aquatic organisms. The results indicated a low potential risk of carbamazepine even under the worst case exposure scenario. Given the dilution factors that affect environmental releases, the risk of exposure to carbamazepine will be even more reduced.

Evaluation of the Scent Collection System for Its Effectiveness in Volatile Organic Compound Collection and Use in Canine Training

As a result of increased terrorist activity around the world, the development of a canine training aid suitable for daily military operations is necessary to provide effective canine explosive detection. Since the use of sniffer dogs has proven to be a reliable resource for the rapid detection of explosive volatiles organic compounds, the present study evaluated the ability of the Human Scent Collection System (HSCS) device for the creation of training aids for plasticized / tagged explosives, nitroglycerin and TNT containing explosives, and smokeless powders for canine training purposes. Through canine field testing, it was demonstrated that volatiles dynamically collected from real explosive material provided a positive canine response showing the effectiveness of the HSCS in creating canine training aids that can be used immediately or up to several weeks (3) after collection under proper storage conditions. These reliable non-hazardous training aids allow its use in areas where real explosive material aids are not practical and/or available.

The effect of weathering processes on the vertical turbulent dispersion characteristics of crude oil spilled on the sea

Since the Exxon Valdez accident in 1987, renewed interest has come forth to better understand and predict the fate and transport of crude oil lost to marine environments. The short-term fate of an Arabian Crude oil was simulated in laboratory experiments using artificial seawater. The time-dependent changes in the rheological and chemical properties of the oil under the influence of natural weathering processes were characterized, including dispersion behavior of the oil under simulated ocean turbulence. Methodology included monitoring the changes in the chemical composition of the oil by Gas Chromatography/Mass Spectrometry (GCMS), toxicity evaluations for the oil dispersions by Microtox analysis, and quantification of dispersed soluble aromatics by fluorescence spectrometry. Results for this oil show a sharp initial increase in viscosity, due to evaporative losses of lower molecular weight hydrocarbons, with the formation of stable water-in-oil emulsions occurring within one week. Toxicity evaluations indicate a decreased EC-50 value (higher toxicity) occurring after the oil has weathered eight hours, with maximum toxicity being observed after weathering seven days. Particle charge distributions, determined by electrophoretic techniques using a Coulter DELSA 440, reveal that an unstable oil dispersion exists within the size range of 1.5 to 2.5 um, with recombination processes being observed between sequential laser runs of a single sample.

(Table T1) N-alkane, n-alcohol and n-fatty acid concentrations in ODP Site 184-1147 and 184-1148 sediments

Lipid compositions of sediments recovered during Ocean Drilling Program Leg 184 in the South China Sea have been identified and quantified. The identified lipids can be ascribed to terrigenous and marine sources. Terrigenous lipids are mainly C27, C29, C31 n-alkanes, C26, C28, C30 n-fatty acids, and n-alcohols, which were derived from leaf waxes of higher land plants and transported to the sea by airborne dust or fresh water. Marine lipids, mainly C37 and C38 alkenones, C30 diol, and C30 and C32 keto-ols, were from microalgae, notably haptophytes and eustigmatophytes. Elevated concentrations and accumulation rates of both terrigenous and marine lipids in the interval 202-245 meters composite depth (mcd) and 0-166 mcd were postulated to be related to the development of the East Asian monsoon at 6-8 Ma and enhanced variations of the developed East Asian monsoon after 3.2 Ma, respectively. The pronounced late Oligocene input of terrigenous lipids reflects the paleoenvironment of a newly opened, narrow basin, with restricted ocean waters and the proximity of continental runoff.

Estudo da capacidade de remoção de óleo solúvel, em águas produzidas, por bentonitas hidrofobizadas

In this study we evaluated the capacity removal of PAHs in an oily solution between the bentonite hydrofobized with linseed oil and paraffin with natural bentonite. Analyses of natural bentonite and hydrofobized were made by the characterization techniques: (1) Thermogravimetric Analysis (TGA), which aimed to evaluate the thermal events due to mass loss, both associated with the exit of moisture and decomposition of clay as due to hidrofobizante loss agent. (2) Analysis of X-ray diffraction (XRD) in order to determine the mineralogical phases that make up the structure of clay and (3) Spectrophotometry in the infrared region used to characterize the functional groups of both the matrix mineral (bentonite) and the hidrofobizantes agents (linseed oil and paraffin). We used a factorial design 24 with the following factors; hidrofobizante, percent hidrofobizante, adsorption time and volume of the oily solution. Analyzing the factorial design 24 was seen that none of the factors apparently was more important than the others and, as all responses showed significant values in relation to the ability of oil removal was not possible to evaluate a difference in the degree of efficiency the two hidrofobizantes. For the new study compared the efficiency of the modified clay, with each hidrofobizante separately in relation to their natural form. As such, there are four new factorial designs 23 using natural bentonite as a differentiating factor. The factors used were bentonite (with and without hydrophobization), exposure time of the adsorbent material to the oily solution and volume of an oily solution, trying to interpret how these factors could influence the process of purifying water contaminated with PAHs. Was employed as a technique for obtaining responses to fluorescence spectroscopy, as already known from literature that PAHs, for presenting combined chains due to condensation of the aromatic rings fluoresce quite similar when excited in the ultraviolet region and as an auxiliary technique to gas chromatography / mass spectrometry (GC-MS) used for the analysis of PAHs in order to complement the study of fluorescence spectroscopy, since the spectroscopic method only allows you an idea of total number of fluorescent species contained in the oil soluble. The result shows an excellent adsorption of PAHs and other fluorescent species assigned to the main effect of the first factor, hydrophobization for the first planning 23 BNTL 5%, for 93% the sixth stop in the second test (+-+),factorial design 23 BNTL 10%, the fourth test (++-) with 94.5% the third factorial design 23 BNTP 5%, the second test (+--) with 91% and the fourth and final planning 23 BNTP 10%, the last test ( + + +) with 88%. Compared with adsorption of bentonite in its natural form. This work also shows the maximum adsorption of each hidrofobizante

Desenvolvimento biotecnológico de uma emulsão de uso tópico a base de óleo de rã-touro Rana catesbeiana Shaw

The skin is one of the largest organs of the human body and accounts for about 16% of body weight. The body protection against the external environment microorganisms is one of its most important functions, however is necessary that the skin remain intact for this function be exercised, so that when there is an injury on the skin, the process of restructuring needs to be starts, however this restructuration may also be compromised due to some diseases, justifying even more the need for the development of topical products that promote or accelerate the skin healing. Thus the aim of this study was to extract bullfrog oil and to develop a suitable topical emulsion. Two different oil samples were extracted by hot or organic solvent process. Titration techniques and gas chromatography- mass spectrometry were used to characterize the bullfrog oil. The required hydrophile-lipophile balance (HLBr) of bullfrog oil was determined and a pseudo-ternary phase diagram was constructed. The stability of the topical emulsion was evaluated. Then, cellular viability was determined by MTT assay using normal fibroblasts (3T3) and melanoma (B16F10) cells lines. The hot extraction yield was 60.6%. The major polyunsaturated compounds found were Eicosapentaenoic acid (17.6%) and Arachidonic acid (8.4%). HLBr study demonstrated the presence of stable systems with HLB ranging from 12.1 to 13.5 and the pseudo-ternary phase diagram showed mainly emulsion systems (62%). Topical emulsion showed 390 nm, polydispersity 0.05, zeta potential -25 mV and remained stable for ninety days. The bullfrog oil and topical emulsion did not showed citotoxicity in normal fibroblasts cells. However, these systems showed significantly inhibition of melanoma cells growth. In conclusion, the bullfrog oil presented desirable chemical characteristics required to be used for the development of a pharmaceutical and cosmetic products.

Concentrations of IPSO25 in surface sediments from coastal and near-coastal Antarctic locations

The presence of a di-unsaturated highly branched isoprenoid (HBI) lipid biomarker (diene II) in Southern Ocean sediments has previously been proposed as a proxy measure of palaeo Antarctic sea ice. Here we show that a source of diene II is the sympagic diatom Berkeleya adeliensis Medlin. Furthermore, the propensity for B. adeliensis to flourish in platelet ice is reflected by an offshore downward gradient in diene II concentration in >100 surface sediments from Antarctic coastal and near-coastal environments. Since platelet ice formation is strongly associated with super-cooled freshwater inflow, we further hypothesize that sedimentary diene II provides a potentially sensitive proxy indicator of landfast sea ice influenced by meltwater discharge from nearby glaciers and ice shelves, and re-examination of some previous diene II downcore records supports this hypothesis. The term IPSO25-Ice Proxy for the Southern Ocean with 25 carbon atoms-is proposed as a proxy name for diene II.

Sediment and pore water chemistry of cores 214 and 755 recovered during Meteor M72/1 and POSEIDON cruise POS317/2, northwestern Black Sea

High-resolution sedimentary records of major and minor elements (Al, Ba, Ca, Sr, Ti), total organic carbon (TOC), and profiles of pore water constituents (SO42-, CH4, Ca2+, Ba2+, Mg2+, alkalinity) were obtained for two gravity cores (core 755, 501 m water depth and core 214, 1686 m water depth) from the northwestern Black Sea. The records were examined in order to gain insight into the cycling of Ba in anoxic marine sediments characterized by a shallow sulfate-methane transition (SMT) as well as the applicability of barite as a primary productivity proxy in such a setting. The Ba records are strongly overprinted by diagenetic barite (BaSO4) precipitation and remobilization; authigenic Ba enrichments were found at both sites at and slightly above the current SMT. Transport reaction modeling was applied to simulate the migration of the SMT during the changing geochemical conditions after the Holocene seawater intrusion into the Black Sea. Based on this, sediment intervals affected by diagenetic Ba redistribution were identified. Results reveal that the intense overprint of Ba and Baxs (Ba excess above detrital average) strongly limits its correlation to primary productivity. These findings have implications for other modern and ancient anoxic basins, such as sections covering the Oceanic Anoxic Events for which Ba is frequently used as a primary productivity indicator. Our study also demonstrates the limitations concerning the use of Baxs as a tracer for downward migrations of the SMT: due to high sedimentation rates at the investigated sites, diagenetic barite fronts are buried below the SMT within a relatively short period. Thus, 'relict' barite fronts would only be preserved for a few thousands of years, if at all.

Chemical composition and stable sulfur isotope record of Black Sea sediments

The main terminal processes of organic matter mineralization in anoxic Black Sea sediments underlying the sulfidic water column are sulfate reduction in the upper 2-4 m and methanogenesis below the sulfate zone. The modern marine deposits comprise a ca. 1-m-deep layer of coccolith ooze and underlying sapropel, below which sea water ions penetrate deep down into the limnic Pleistocene deposits from >9000 years BP. Sulfate reduction rates have a subsurface maximum at the SO4[2-]-CH4 transition where H2S reaches maximum concentration. Because of an excess of reactive iron in the deep limnic deposits, most of the methane-derived H2S is drawn downward to a sulfidization front where it reacts with Fe(III) and with Fe2+ diffusing up from below. The H2S-Fe2+ transition is marked by a black band of amorphous iron sulfide above which distinct horizons of greigite and pyrite formation occur. The pore water gradients respond dynamically to environmental changes in the Black Sea with relatively short time constants of ca. 500 yr for SO4[2-] and 10 yr for H2S, whereas the FeS in the black band has taken ca. 3000 yr to accumulate. The dual diffusion interfaces of SO4[2-]-CH4 and H2S-Fe2+ cause the trapping of isotopically heavy iron sulfide with delta34S = +15 to +33 per mil at the sulfidization front. A diffusion model for sulfur isotopes shows that the SO4[2-] diffusing downward into the SO4[2-]-CH4 transition has an isotopic composition of +19 per mil, close to the +23 per mil of H2S diffusing upward. These isotopic compositions are, however, very different from the porewater SO4[2-] (+43 per mil) and H2S (-15 per mil) at the same depth. The model explains how methane-driven sulfate reduction combined with a deep H2S sink leads to isotopically heavy pyrite in a sediment open to diffusion. These results have general implications for the marine sulfur cycle and for the interpretation of sulfur isotopic data in modern sediments and in sedimentary rocks throughout earth's history.

(Table 1) Sample descriptions and results: Carbon, lipid, and kerogen analyses, at DSDP Leg 64 Holes

Pleistocene sediments in the Guaymas Basin, Gulf of California, have been intruded by sills and their organic matter thus subjected to thermal stress. Sediment samples from DSDP/IPOD Sites 477, 478, and 481, and samples of thermally unaltered materials from Sites 474 and 479 were analyzed to characterize the lipids and kerogens and to evaluate the effects of the intrusive thermal stresses. The lipids of the thermally unaltered samples are derived from microbial and terrestrial higher-plant detritus. The samples from the sill proximities contain the distillates, and those adjacent to the sills contain essentially no lipids. The pyrograms of the kerogens from the unaltered samples reflect their predominantly autochthonous microbial origin. When compared with the unaltered samples, the pyrograms of the altered kerogen samples reflect the thermal effects by a reduction in the complexity of the products. Kerogens adjacent to the sills produced little or no pyrolysis products. The effects of intrusions into unconsolidated, wet sediments resulted in in situ pyrolysis of the organic matter, as confirmed by these data.

GDGT and n-alkane data of sediment core GeoB4901-8

The tight coupling between the atmospheric and oceanic circulation in the equatorial Atlantic region makes this area an important region for paleoclimatic research. Previous studies report the occurrence of large amounts of terrigenous material and soil organic carbon (SOC) within the marine sediments of the eastern Gulf of Guinea. We use the accumulation rates (AR) of branched glycerol dialkyl glycerol tetraethers (GDGTs) to identify variations in SOC delivery to the Niger Fan over the last 35 ka, and compare these records to long-chain n-alkanes as a proxy for higher plant material, to an inorganic proxy for terrigenous input (aluminum AR) and to indicators for the marine productivity (AR of carbonate and crenarchaeol). In addition, sea surface temperatures (SSTs) are calculated based on the TEX86H index and environmental factors affecting the SST-reconstructions are discussed. Our results indicate that Al AR are closely connected to the rate of mean sea level change after 15 ka BP, with an additional influence of the increased monsoonal precipitation and extended vegetation cover corresponding to the African Humid Period (14.8-5.5 ka BP). Branched GDGT AR appears to be determined by shelf erosion in addition to the interplay of monsoonal precipitation and vegetation cover controlling soil erosion. Long-chain n-alkane concentrations clearly show a different trend than the other proxies, which might be due to their predominant eolian transport. Paleo-SSTs show a clear shift from colder temperatures during the last glacial period (20-22 °C) to warmer temperatures during the Holocene (24-26 °C). However, TEX86H-based SSTs are cold-biased compared to recent SSTs and Mg/Ca-based SST reconstructions, which is probably caused by a high seasonality of the Thaumarchaeota, with a maximum productivity of these organisms during the cold summer months. However, a sub-surface production of GDGTs and/or a potential bias of SST reconstruction by terrestrial input could not be completely excluded.