Block Copolymers Containing (R)-3-Hydroxybutyrate and Isosorbide Succinate or (S)-Lactic Acid Mers

A new aliphatic block copolyester was synthesized in bulk from transesterification techniques between poly((R)-3-hydroxybutyrate) (PHB) and poly(isosorbide succinate) (PIS). Additionally, other two block copolyesters were synthesized in bulk either from transesterification reactions involving PHB and poly(l-lactide) (PLLA) or from ring-opening copolymerization of l-lactide and hydroxyl-terminated PHB, as result of a previous transesterification reactions with isosorbide. Two-component blends of PHB and PIS or PLLA were also prepared as comparative systems. SEC, MALDI-TOF mass spectrometry (MALDI-TOFMS), ¹H and ¹³C NMR spectroscopy, WAXD, solubility tests, and TG thermal analysis were used for characterization. The block copolymer structures of the products were evidenced by MALDI-TOFMS, ¹³C NMR, and WAXD data. The block copolymers and the corresponding binary blends presented different solubility properties, as revealed by solubility tests. Although the incorporation of PIS sequences into PHB main backbone did not enhance the thermal stability of the product, it reduced its crystallinity, which could be advantageous for faster biodegradation rate. These products, composed of PHB and PIS or PLLA sequences, are an interesting alternative in biomedical applications.     

Ecologically Functional Floodplains: Connectivity,Flow Regime,and Scale1

Opperman, Jeffrey J., Ryan Luster, Bruce A. McKenney, Michael Roberts, and Amanda Wrona Meadows, 2010. Ecologically Functional Floodplains: Connectivity, Flow Regime, and Scale. Journal of the American Water Resources Association (JAWRA) 46(2):211-226. DOI: 10.1111/j.1752-1688.2010.00426.x Abstract: This paper proposes a conceptual model that captures key attributes of ecologically functional floodplains, encompassing three basic elements: (1) hydrologic connectivity between the river and the floodplain, (2) a variable hydrograph that reflects seasonal precipitation patterns and retains a range of both high and low flow events, and (3) sufficient spatial scale to encompass dynamic processes and for floodplain benefits to accrue to a meaningful level. Although floodplains support high levels of biodiversity and some of the most productive ecosystems on Earth, they are also among the most converted and threatened ecosystems and therefore have recently become the focus of conservation and restoration programs across the United States and globally. These efforts seek to conserve or restore complex, highly variable ecosystems and often must simultaneously address both land and water management. Thus, such efforts must overcome considerable scientific, technical, and socioeconomic challenges. In addition to proposing a scientific conceptual model, this paper also includes three case studies that illustrate methods for addressing these technical and socioeconomic challenges within projects that seek to promote ecologically functional floodplains through river-floodplain reconnection and/or restoration of key components of hydrological variability.     

Source apportionment of wintertime secondary organic aerosol during the California regional PM10/PM2.5 air quality study

The UCD/CIT air quality model with the Caltech Atmospheric Chemistry Mechanism (CACM) was used to predict source contributions to secondary organic aerosol (SOA) formation in the San Joaquin Valley (SJV) from December 15, 2000 to January 7, 2001. The predicted 24-day average SOA concentration had a maximum value of 4.26 μg m^?3 50 km southwest of Fresno. Predicted SOA concentrations at Fresno, Angiola, and Bakersfield were 2.46 μg m^?3, 1.68 μg m^?3, and 2.28 μg m^?3, respectively, accounting for 6%, 37%, and 4% of the total predicted organic aerosol. The average SOA concentration across the entire SJV was 1.35 μg m^?3, which accounts for approximately 20% of the total predicted organic aerosol. Averaged over the entire SJV, the major SOA sources were solvent use (28% of SOA), catalyst gasoline engines (25% of SOA), wood smoke (16% of SOA), non-catalyst gasoline engines (13% of SOA), and other anthropogenic sources (11% of SOA). Diesel engines were predicted to only account for approximately 2% of the total SOA formation in the SJV because they emit a small amount of volatile organic compounds relative to other sources. In terms of SOA precursors within the SJV, long-chain alkanes were predicted to be the largest SOA contributor, followed by aromatic compounds. The current study identifies the major known contributors to the SOA burden during a winter pollution episode in the SJV, with further enhancements possible as additional formation pathways are discovered.     

Aerosol speciation and mass prediction from toluene oxidation under high NOx conditions

A kinetically based gas-particle partitioning box model is used to highlight the importance of parameter representation in the prediction of secondary organic aerosol (SOA) formation following the photo-oxidation of toluene. The model is initialized using experimental data from York University's indoor smog chamber and provides a prediction of the total aerosol yield and speciation. A series of model sensitivity experiments were performed to study the aerosol speciation and mass prediction under high NO_x conditions (VOC/NO_x = 0.2). Sensitivity experiments indicate vapour pressure estimation to be a large area of weakness in predicting aerosol mass, creating an average total error range of 70 μg m^?3 (range of 5–145 μg m^?3), using two different estimation methods. Aerosol speciation proved relatively insensitive to changes in vapour pressure. One species, 3-methyl-6-nitro-catechol, dominated the aerosol phase regardless of the vapour pressure parameterization used and comprised 73–88% of the aerosol by mass. The dominance is associated with the large concentration of 3-methyl-6-nitro-catechol in the gas-phase. The high NO_x initial conditions of this study suggests that the predominance of 3-methyl-6-nitro-catechol likely results from the cresol-forming branch in the Master Chemical Mechanism taking a significant role in secondary organic aerosol formation under high NO_x conditions. Further research into the yields and speciation leading to this reaction product is recommended.     

Theoretical versus observed gas-particle partitioning of carbonyl emissions from motor vehicles

A state-of-the-science thermodynamic model describing gas-particle absorption processes was used to predict the gas-particle partitioning of mixtures of approximately 60 carbonyl compounds emitted from low-emission gasoline-powered vehicles, three-way catalyst gasoline-powered vehicles, heavy-duty diesel vehicles under the idle-creep condition (HDDV idle), and heavy-duty diesel vehicles under the five-mode test (HDDV 5-mode). Exhaust was diluted by a factor of 120-580 with a residence time of approximately 43 sec. The predicted equilibrium absorption partitioning coefficients differed from the measured partitioning coefficients by several orders of magnitude. Time scales to reach equilibrium in the dilution sampling system were close to the actual residence time during the HDDV 5-mode test and much longer than the actual residence time during the other vehicle tests. It appears that insufficient residence time in the sampling system cannot uniformly explain the failure of the absorption mechanism to explain the measured partitioning. Other gas-particle partitioning mechanisms (e.g., heterogeneous reactions, capillary adsorption) beyond the simple absorption theory are needed to explain the discrepancy between calculated carbonyl partitioning coefficients and observed partitioning. Both of these alternative partitioning mechanisms imply great challenges for the measurement and modeling of semi-volatile primary organic aerosol (POA) species from motor vehicles. Furthermore, as emitted particle concentrations from newer vehicles approach atmospheric background levels, dilution sampling systems must fundamentally change their approach so that they use realistic particle concentrations in the dilution air to approximately represent real-world conditions. Samples collected with particle-free dilution air yielding total particulate matter concentrations below typical ambient concentrations will not provide a realistic picture of partitioning for semi-volatile compounds.     

Influence of regional development policies and clean technology adoption on future air pollution exposure

Future air pollution emissions in the year 2030 were estimated for the San Joaquin Valley (SJV) in central California using a combined system of land use, mobile, off-road, stationary, area, and biogenic emissions models. Four scenarios were developed that use different assumptions about the density of development and level of investment in transportation infrastructure to accommodate the expected doubling of the SJV population in the next 20 years. Scenario 1 reflects current land-use patterns and infrastructure while scenario 2 encouraged compact urban footprints including redevelopment of existing urban centers and investments in transit. Scenario 3 allowed sprawling development in the SJV with reduced population density in existing urban centers and construction of all planned freeways. Scenario 4 followed currently adopted land use and transportation plans for the SJV. The air quality resulting from these urban development scenarios was evaluated using meteorology from a winter stagnation event that occurred on December 15th, 2000 to January 7th 2001. Predicted base-case PM2.5 mass concentrations within the region exceeded 35 μg m^?3 over the 22-day episode. Compact growth reduced the PM2.5 concentrations by ～1 μg m^?3 relative to the base-case over most of the SJV with the exception of increases (～1 μg m^?3) in urban centers driven by increased concentrations of elemental carbon (EC) and organic carbon (OC). Low-density development increased the PM2.5 concentrations by 1–4 μg m^?3 over most of the region, with decreases (0.5–2 μg m^?3) around urban areas. Population-weighted average PM2.5 concentrations were very similar for all development scenarios ranging between 16 and 17.4 μg m^?3. Exposure to primary PM components such as EC and OC increased 10–15% for high density development scenarios and decreased by 11–19% for low-density scenarios. Patterns for secondary PM components such as nitrate and ammonium ion were almost exactly reversed, with a 10% increase under low-density development and a 5% decrease under high density development. The increased human exposure to primary pollutants such as EC and OC could be predicted using a simplified analysis of population-weighted primary emissions. Regional planning agencies should develop thresholds of population-weighted primary emissions exposure to guide the development of growth plans. This metric will allow them to actively reduce the potential negative impacts of compact growth while preserving the benefits.     

Evaluating Conservation Program Success with Landsat and SWAT

In the United States, many state and federally funded conservation programs are required to quantify the water quality benefits resulting from their efforts. The objective of this research was to evaluate the impact of conservation practices subsidized by the Oklahoma Conservation Commission on phosphorus and sediment loads to Lake Wister. Conservation practices designed to increase vegetative cover in grazed pastures were evaluated using Landsat imagery and the Soil and Water Assessment Tool (SWAT). Several vegetative indices were derived from Landsat imagery captured before and after the implementation of conservation practices. Collectively, these indicators provided an estimate of the change in vegetative soil cover attributable to conservation practices in treated fields. Field characteristics, management, and changes in vegetative cover were used in the SWAT model to simulate sediment and phosphorus losses before and after practice implementation. Overall, these conservation practices yielded a 1.9% improvement in vegetative cover and a predicted sediment load reduction of 3.5%. Changes in phosphorus load ranged from a 1.0% improvement to a 3.5% increase, depending upon initial vegetative conditions. The use of fertilizers containing phosphorus as a conservation practice in low-productivity pastures was predicted by SWAT to increase net phosphorus losses despite any improvement in vegetative cover. This combination of vegetative cover analysis and hydrologic simulation was a useful tool for evaluating the effects of conservation practices at the basin scale and may provide guidance for the selection of conservation measures subsidized in future conservation programs.     

Better than their reputation: enhancing the validity of contingent valuation mail survey results through citizen expert groups

Although contingent valuation is the dominant technique for the valuation of public projects, especially in the environmental sector, the high costs of contingent valuation surveys prevent the use of this method for the assessment of relatively small projects. The reason for this cost problem is that typically only contingent valuation studies which are based on face-to-face interviews are accepted as leading to valid results. Particularly in countries with high wages, face-to-face surveys are extremely costly considering that for a valid contingent valuation study a minimum of 1000 completed face-to-face interviews is required. This paper tries a rehabilitation of mail surveys as low-budget substitutes for costly face-to-face surveys. Based on an empirical contingent valuation study in Northern Thailand, it is shown that the validity of mail surveys can be improved significantly if so-called Citizen Expert Groups are employed for a thorough survey design.     

Reply to Discussion1 - by George Ice,George Brown,John Gravelle,C. Rhett Jackson,Jeff Light,Timothy Link,Douglas Martin,Dale McGreer,and Arne Skaugset2 “Stream Temperature Relationships to Forest Harvest in Western Washington”3

Pollock, Michael M. and Timothy J. Beechie, 2010. Reply to Discussion –“Stream Temperature Relationships to Forest Harvest in Western Washington” by George Ice, George Brown, John Gravelle, C. Rhett Jackson, Jeff Light, Timothy Link, Douglas Martin, Dale McGreer, and Arne Skaugset. Journal of the American Water Resources Association (JAWRA) 46(4): 843-847. DOI: 10.1111/j.1752-1688.2010.00456.x     

Comparison of selected nutrients and bacteria from common contiguous soils inside and outside swine lagoon effluent spray fields after long-term use

Swine (Sus scofa domestica) lagoon effluent is a valuable resource. In the U.S. Mid-South it is applied from April to September to fertilize grass hay in spray-irrigated fields. Lagoon levels of nutrients and bacteria, and soil levels of nutrients have been documented, but little was known of effluent bacterial levels in soil. The present study examined levels of selected effluent bacteria and nutrients in soils inside and outside spray fields after >15 yr of effluent irrigation. Samples were collected February to March 2009 from contiguous soils spanning adjacent irrigated and nonirrigated areas. Separate soil cores for bacterial and nutrient tests were collected in pairs <10 cm apart. Five cores each were collected at 15-m intervals and combined, respectively, to comprise inside and outside samples from each of 20 soils (four each from five farms/spray fields). Analyses of data combined across all soils showed higher pH and Mehlich-3-extracrable (M3-) P, Mg, K, Na, Cu, and Zn inside than outside spray fields, while total N, total C, M3-Ca, and M3-Mn did not differ. Bacterial levels were higher inside than outside spray fields for heterotrophic plate counts, thermotolerant coliforms, Staphylococcus spp., and Clostridium perfringens, but levels of Escherichia coli and Enterococcus spp. were not different. Cultural presence/absence tests for three pathogens (Listeria spp., Campylobacter spp., and Salmonella spp.) detected only Listeria spp., which did not differ inside (23% positive samples) and outside (28% positive). Molecular tests detected all three pathogens at low levels that were not different inside and outside. We found no evidence of cumulative buildup of Campylobacter spp., Listeria spp., or Salmonela s. in spray field soils.