Pyrolysis of peptides and proteins. Analytical study and environmental applications

Analytical pyrolysis was used to investigate the formation of diketopiperazines (DKPs) which are cyclic dipeptides formed from the thermal degradation of proteins. A quali/quantitative procedure was developed combining microscale flash pyrolysis at 500 °C with gas chromatography-mass spectrometry (GC-MS) of DKPs trapped onto an adsorbent phase. Polar DKPs were silylated prior to GC-MS. Particular attention was paid to the identification of proline (Pro) containing DKPs due to their greater facility of formation. The GC-MS characteristics of more than 80 original and silylated DKPs were collected from the pyrolysis of sixteen linear dipeptides and four model proteins (e.g. bovine serum albumin, BSA). The structure of a novel DKP, cyclo(pyroglutamic-Pro) was established by NMR and ESI-MS analysis, while the structures of other novel DKPs remained tentative. DKPs resulted rather specific markers of amino acid sequence in proteins, even though the thermal degradation of DKPs should be taken into account. Structural information of DKPs gathered from the pyrolysis of model compounds was employed to the identification of these compounds in the pyrolysate of proteinaceous samples, including intrinsecally unfolded protein (IUP). Analysis of the liquid fraction (bio-oil) obtained from the pyrolysis of microalgae Nannochloropsis gaditana, Scenedesmus spp with a bench scale reactor showed that DKPs constituted an important pool of nitrogen-containing compounds. Conversely, the level of DKPs was rather low in the bio-oil of Botryococcus braunii. The developed micropyrolysis procedure was applied in combination with thermogravimetry (TGA) and infrared spectroscopy (FT-IR) to investigate surface interaction between BSA and synthetic chrysotile. The results showed that the thermal behavior of BSA (e.g. DKPs formation) was affected by the different form of doped synthetic chrysotile. The typical DKPs evolved from collagen were quantified in the pyrolysates of archaeological bones from Vicenne Necropolis in order to evaluate their conservation status in combination with TGA, FTIR and XRD analysis.

Relationships between plant diversity and environmental heterogeneity in rupicolous grasslands on gypsum. The case study of Alysso-Sedion albi (Habitat 6110).

Plant communities on weathered rock and outcrops are characterized by high values in species richness (Dengler 2006) and often persist on small and fragmented surfaces. Yet very few studies have examined the relationships between heterogeneity and plant diversity at small scales, in particular in poor-nutrient and low productive environment (Shmida and Wilson 1985, Lundholm 2003). In order to assess these relationships both in space and time in relationship, two different approaches were employed in the present study, in two gypsum outcrops of Northern Apennine. Diachronic and synchronic samplings from April 2012 to March 2013 were performed. A 50x50 cm plot was used in both samplings such as the sampling unit base. The diachronic survey aims to investigate seasonal patterning of plant diversity by the use of images analysis techniques integrated with field data and considering also seasonal climatic trend, the substrate quality and its variation in time. The purpose of the further, synchronic sampling was to describe plant diversity pattern as a function of the environmental heterogeneity meaning in substrate typologies, soil depth and topographic features. Results showed that responses of diversity pattern depend both on the resources availability, environmental heterogeneity and the manner in which the different taxonomic group access to them during the year. Species richness and Shannon diversity were positively affected by increasing in substrate heterogeneity. Furthermore a good turnover in seasonal species occurrence was detected. This vegetation may be described by the coexistence of three groups of species which created a gradient from early colonization stages, characterized by greater slope and predominance of bare rock, gradually to situation of more developed soil.

Design and prototyping of electronic PCBs for the study of the atmosphere in harsh environmental conditions

Progettazione, test e creazione di schede elettroniche per lo studio dell'atmosfera in condizioni ambientali difficili.

Inequity Measures for Evaluations of Environmental Justice: A Case Study of Close Proximity to Highways in NYC

Assessments of environmental and territorial justice are similar in that both assess whether empirical relations between the spatial arrangement of undesirable hazards (or desirable public goods and services) and socio-demographic groups are consistent with notions of social justice, evaluating the spatial distribution of benefits and burdens (outcome equity) and the process that produces observed differences (process equity. Using proximity to major highways in NYC as a case study, we review methodological issues pertinent to both fields and discuss choice and computation of exposure measures, but focus primarily on measures of inequity. We present inequity measures computed from the empirically estimated joint distribution of exposure and demographics and compare them to traditional measures such as linear regression, logistic regression and Theil’s entropy index. We find that measures computed from the full joint distribution provide more unified, transparent and intuitive operational definitions of inequity and show how the approach can be used to structure siting and decommissioning decisions.

EPA's Council for Regulatory Environmental Modeling : a case study of science policy implementation

As environmental problems became more complex, policy and regulatory decisions become far more difficult to make. The use of science has become an important practice in the decision making process of many federal agencies. Many different types of scientific information are used to make decisions within the EPA, with computer models becoming especially important. Environmental models are used throughout the EPA in a variety of contexts and their predictive capacity has become highly valued in decision making. The main focus of this research is to examine the EPA’s Council for Regulatory Modeling (CREM) as a case study in addressing science issues, particularly models, in government agencies. Specifically, the goal was to answer the following questions: What is the history of the CREM and how can this information shed light on the process of science policy implementation? What were the goals of implementing the CREM? Were these goals reached and how have they changed? What have been the impediments that the CREM has faced and why did these impediments occur? The three main sources of information for this research came from observations during summer employment with the CREM, document review and supplemental interviews with CREM participants and other members of the modeling community. Examining a history of modeling at the EPA, as well as a history of the CREM, provides insight into the many challenges that are faced when implementing science policy and science policy programs. After examining the many impediments that the CREM has faced in implementing modeling policies, it was clear that the impediments fall into two separate categories, classic and paradoxical. The classic impediments include the more standard impediments to science policy implementation that might be found in any regulatory environment, such as lack of resources and changes in administration. Paradoxical impediments are cyclical in nature, with no clear solution, such as balancing top-down versus bottom-up initiatives and coping with differing perceptions. These impediments, when not properly addressed, severely hinder the ability for organizations to successfully implement science policy.

An examination of the Gonorrhea Cases & Places Study: An analysis of the Theory of Gender and Power, Situational/Environmental Variables Theory, and Sexual Script Theory as it relates to risky sexual behavior in African American adults

Objective. The purpose of the study is to provide a holistic depiction of behavioral & environmental factors contributing to risky sexual behaviors among predominantly high school educated, low-income African Americans residing in urban areas of Houston, TX utilizing the Theory of Gender and Power, Situational/Environmental Variables Theory, and Sexual Script Theory. Methods. A cross-sectional study was conducted via questionnaires among 215 Houston area residents, 149 were women and 66 were male. Measures used to assess behaviors of the population included a history of homelessness, use of crack/cocaine among several other illicit drugs, the type of sexual partner, age of participant, age of most recent sex partner, whether or not participants sought health care in the last 12 months, knowledge of partner's other sexual activities, symptoms of depression, and places where partner's were met. In an effort to determine risk of sexual encounters, a risk index employing the variables used to assess condom use was created categorizing sexual encounters as unsafe or safe. Results. Variables meeting the significance level of p<.15 for the bivariate analysis of each theory were entered into a binary logistic regression analysis. The block for each theory was significant, suggesting that the grouping assignments of each variable by theory were significantly associated with unsafe sexual behaviors. Within the regression analysis, variables such as sex for drugs/money, low income, and crack use demonstrated an effect size of ≥ ± 1, indicating that these variables had a significant effect on unsafe sexual behavioral practices. Conclusions. Variables assessing behavior and environment demonstrated a significant effect when categorized by relation to designated theories.

Late Glacial and Holocene environmental history of the Pirin Mountains (SW Bulgaria): a paleolimnological study of Lake Dalgoto (2310 m)

Diatoms, Cladocera, and chironomids preserved in the sediments of Lake Dalgoto were studied to reconstruct the history of the lake ecosystem in the context of the vegetation history as represented by the pollen stratigraphy. Younger Dryas silty sediments at the base of the core are characterized by low diversity of aquatic organisms. The transition to the Holocene is indicated by a sharp change from silt to clay-gyttja. The migration and expansion of trees at lower elevations between 10200 and 8500 14C-yr BP, along with higher diversities and concentrations of aquatic organisms and the decreased proportion of north-alpine diatoms, point to rapidly rising summer temperatures. After 6500 14C-yr BP the expansion of Pinus mugo in the catchment coincides with signs of natural eutrophication as recorded by an increase of planktonic diatoms. In the late Holocene (4000–0 14C-yr BP) Pinus peuce and Abies are reduced and Picea expands. Cereal grains and disturbance indicators suggest late-Holocene human modification of the vegetation.

An examination of the Gonorrhea Cases & Places study: An analysis of the Theory of Gender and Power, Situational/Environmental Variables Theory, and Sexual Script Theory as it relates to risky sexual behavior in African American adults

Objective. The purpose of the study is to provide a holistic depiction of behavioral & environmental factors contributing to risky sexual behaviors among predominantly high school educated, low-income African Americans residing in urban areas of Houston, TX utilizing the Theory of Gender and Power, Situational/Environmental Variables Theory, and Sexual Script Theory. ^ Methods. A cross-sectional study was conducted via questionnaires among 215 Houston area residents, 149 were women and 66 were male. Measures used to assess behaviors of the population included a history of homelessness, use of crack/cocaine among several other illicit drugs, the type of sexual partner, age of participant, age of most recent sex partner, whether or not participants sought health care in the last 12 months, knowledge of partner's other sexual activities, symptoms of depression, and places where partner's were met. In an effort to determine risk of sexual encounters, a risk index employing the variables used to assess condom use was created categorizing sexual encounters as unsafe or safe. ^ Results. Variables meeting the significance level of p<.15 for the bivariate analysis of each theory were entered into a binary logistic regression analysis. The block for each theory was significant, suggesting that the grouping assignments of each variable by theory were significantly associated with unsafe sexual behaviors. Within the regression analysis, variables such as sex for drugs/money, low income, and crack use demonstrated an effect size of ≥±1, indicating that these variables had a significant effect on unsafe sexual behavioral practices. ^ Conclusions. Variables assessing behavior and environment demonstrated a significant effect when categorized by relation to designated theories. ^

THE CHLOREX TREATABILITY STUDY: ENVIRONMENTAL FATE IN FACULTATIVE ANAEROBIC AND AEROBIC WASTE STABILIZATION PONDS (BIODEGRADATION, VOLATILIZATION, SORPTION, PRIORITY POLLUTANTS)

The efficacy of waste stabilization lagoons for the treatment of five priority pollutants and two widely used commercial compounds was evaluated in laboratory model ponds. Three ponds were designed to simulate a primary anaerobic lagoon, a secondary facultative lagoon, and a tertiary aerobic lagoon. Biodegradation, volatilization, and sorption losses were quantified for bis(2-chloroethyl) ether, benzene, toluene, naphthalene, phenanthrene, ethylene glycol, and ethylene glycol monoethyl ether. A statistical model using a log normal transformation indicated biodegradation of bis(2-chloroethyl) ether followed first-order kinetics. Additionally, multiple regression analysis indicated biochemical oxygen demand was the water quality variable most highly correlated with bis(2-chloroethyl) ether effluent concentration. ^

Molecular dissolved organic matter composition and environmental parameters from a laboratory incubation study

Dissolved organic matter (DOM) in the oceans constitutes a major carbon pool involved in global biogeochemical cycles. More than 96% of the marine DOM resists microbial degradation for thousands of years. The composition of this refractory DOM (RDOM) exhibits a molecular signature which is ubiquitously detected in the deep oceans. Surprisingly efficient microbial transformation of labile into RDOM was shown experimentally, implying that microorganisms produce far more RDOM than needed to sustain the global pool. By assessing the microbial formation and transformation of DOM in unprecedented molecular detail for 3 years, we show that most of the newly formed RDOM is molecularly different from deep sea RDOM. Only <0.4% of the net community production was channeled into RDOM molecularly undistinguishable from deep sea DOM. Our study provides novel experimentally derived molecular evidence and data for global models on the production, turnover and accumulation of marine DOM.