Modelling the photooxidation of ULP,E5 and E10 in the CSIRO smog chamber

The photooxidation of fuel vapour was investigated in a smog chamber and simulated using three chemical mechanisms, the Master Chemical Mechanism (MCMv3.1), SAPRC-99 and the Carbon Bond chemical mechanism (CB05). Three varieties of fuel were used, unleaded petrol (ULP) and two ULP-ethanol blends which contained 5% and 10% ethanol (E5, E10). The fuel vapours were introduced into the chamber using two methods, by injecting the vapours from wholly evaporated fuel directly, and by injecting the headspace vapour from fuel equilibrated at 38 °C. The chamber experiments were simulated using the selected mechanisms and comparisons made with collected experimental data.The SAPRC-99 mechanism reproduced Δ(O₃–NO) more accurately for almost all fuel types and injection modes, with negligible model error for both injection modes. The average model error for MCM simulations was ?16% and for CB05 the average model error was ?34%. The predictions for the CB05 mechanism varied depending on injection mode, the Δ(O₃–NO) model error for wholly evaporated experiments was ?44%, compared to ?24% for headspace vapour experiments. The difference in aromatic content between experiments of different injection modes was likely to be the cause of the difference in model error for CB05. The model error for all headspace experiments was dependent upon the initial carbon monoxide concentrations.The results for Δ(O₃–NO) were matched by the prediction of other key products, with formaldehyde predicted to within 20% by both SAPRC and the MCM. The addition of ethanol to the base SAPRC mechanism altered the predictions of Δ(O₃–NO) by less than 2%. Changes observed in the concentrations of formaldehyde and acetaldehyde were consistent with the expected yields from ethanol oxidation.     

Water Quality Functions of a 15-Year-Old Riparian Forest Buffer System1

Newbold, J. Denis, Susan Herbert, Bernard W. Sweeney, Paul Kiry, and Stephen J. Alberts, 2010. Water Quality Functions of a 15-Year-Old Riparian Forest Buffer System. Journal of the American Water Resources Association (JAWRA) 46(2):299-310. DOI: 10.1111/j.1752-1688.2010.00421.x Abstract: We monitored long-term water quality responses to the implementation of a three-zone Riparian Forest Buffer System (RFBS) in southeastern Pennsylvania. The RFBS, established in 1992 in a 15-ha agricultural (row crop) watershed, consists of: Zone 1, a streamside strip (∼10 m wide) of permanent woody vegetation for stream habitat protection; Zone 2, an 18- to 20-m-wide strip reforested in hardwoods upslope from Zone 2; and Zone 3, a 6- to 10-m-wide grass filter strip in which a level lip spreader was constructed. The monitoring design used paired watersheds supplemented by mass balance estimates of nutrient and sediment removal within the treated watershed. Tree growth was initially delayed by drought and deer damage, but increased after more aggressive deer protection (1.5 m polypropylene shelters or wire mesh protectors) was instituted. Basal tree area increased ∼20-fold between 1998 and 2006, and canopy cover reached 59% in 2006. For streamwater nitrate, the paired watershed comparison was complicated by variations in both the reference stream concentrations and in upslope groundwater nitrate concentrations, but did show that streamwater nitrate concentrations in the RFBS watershed declined relative to the reference stream from 2002 through the end of the study in early 2007. A subsurface nitrate budget yielded an average nitrate removal by the RFBS of 90 kg/ha/year, or 26% of upslope subsurface inputs, for the years 1997 through 2006. There was no evidence from the paired watershed comparison that the RFBS affected streamwater phosphorus concentration. However, groundwater phosphorus did decline within the buffer. Overland flow sampling of 23 storms between 1997 and 2006 showed that total suspended solids concentration in water exiting the RFBS to the stream was on average 43% lower than in water entering the RFBS from the tilled field. Particulate phosphorus concentration was lower by 22%, but this removal was balanced by a 26% increase in soluble reactive phosphorus so that there was no net effect on total phosphorus.     

Concentrations of polychlorinated biphenyls in water from US Lake Ontario tributaries between 2004 and 2008

Research on the environmental fate and transport of PCBs in Lake Ontario basin depends, among other aspects, on the availability of representative data sets for upstream sources, but data are lacking for most US Lake Ontario tributaries. In this study, water samples were collected between September 2004 and October 2008 from five tributaries and were analyzed for 209 polychlorinated biphenyls (PCB) with high-resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) following EPA Method 1668A. Total PCB concentrations ranged between 0.31 and 42.75 ng L⁻¹. Congeners between Di and Hexa PCBs accounted between 70 and 99% of the total PCB. The tributary with highest PCB concentrations presented similar pattern and percentage levels to Aroclor 1242. Total average loads for the sampling events ranged between 1.85 g d⁻¹ and 59.08 g d⁻¹. PCB concentrations were evaluated against other variables and other studies (including different matrices) to better understand their transport. The methodology used is reliable to assess PCB contamination in surface water.     

Regional source identification using Lagrangian stochastic particle dispersion and HYSPLIT backward-trajectory models

The main objective of this study was to investigate the capabilities of the receptor-oriented inverse mode Lagrangian Stochastic Particle Dispersion Model (LSPDM) with the 12-km resolution Mesoscale Model 5 (MM5) wind field input for the assessment of source identification from seven regions impacting two receptors located in the eastern United States. The LSPDM analysis was compared with a standard version of the Hybrid Single-Particle Lagrangian Integrated Trajectory (HYSPLIT) single-particle backward-trajectory analysis using inputs from MM5 and the Eta Data Assimilation System (EDAS) with horizontal grid resolutions of 12 and 80 km, respectively. The analysis included four 7-day summertime events in 2002; residence times in the modeling domain were computed from the inverse LSPDM runs and HYPSLIT-simulated backward trajectories started from receptor-source heights of 100, 500, 1000, 1500, and 3000 m. Statistics were derived using normalized values of LSPDM- and HYSPLIT-predicted residence times versus Community Multiscale Air Quality model-predicted sulfate concentrations used as baseline information. From 40 cases considered, the LSPDM identified first- and second-ranked emission region influences in 37 cases, whereas HYSPLIT-MM5 (HYSPLIT-EDAS) identified the sources in 21 (16) cases. The LSPDM produced a higher overall correlation coefficient (0.89) compared with HYSPLIT (0.55-0.62). The improvement of using the LSPDM is also seen in the overall normalized root mean square error values of 0.17 for LSPDM compared with 0.30-0.32 for HYSPLIT. The HYSPLIT backward trajectories generally tend to underestimate near-receptor sources because of a lack of stochastic dispersion of the backward trajectories and to overestimate distant sources because of a lack of treatment of dispersion. Additionally, the HYSPLIT backward trajectories showed a lack of consistency in the results obtained from different single vertical levels for starting the backward trajectories. To alleviate problems due to selection of a backward-trajectory starting level within a large complex set of 3-dimensional winds, turbulence, and dispersion, results were averaged from all heights, which yielded uniform improvement against all individual cases.     

Chest deflections and injuries in oblique lateral impacts

A majority of laboratory-driven side-impact injury assessments are conducted using postmortem human subjects (PMHS) under the pure lateral mode. Because real-world injuries occur under pure and oblique modes, this study was designed to determine chest deflections and injuries using PMHS under the latter mode. Anthropometrical data were obtained and x-rays were taken. Specimens were seated on a sled and lateral impact acceleration corresponding to a change in velocity of 24 km/h was applied such that the vector was at an angle of 20 or 30 degrees. Chestbands were fixed at the level of the axilla (upper), xyphoid process (middle), and tenth rib (lower) location. Deflection contours as a function of time at the levels of the axilla and mid-sternum, representing the thorax, and at the tenth rib level, representing the abdomen, were evaluated for peak magnitudes. All data were normalized using mass-scaling procedures. Injuries were identified following the test at autopsy. Trauma graded according to the Abbreviated Injury Score, 1990 version, indicated primarily unilateral rib fractures and soft tissue abnormalities such as lung contusion and diaphragm laceration occurred. Mean peak deflections at the upper, middle, and lower levels of the chest for the 30-degree tests were 96.2, 78.5, and 76.8 mm. For the 20-degree tests, these magnitudes were 77.5, 89.9, and 73.6 mm. Statistical analysis indicated no significant (p > 0.05) differences in peak chest deflections at all levels between the two obliquities although the metric was significantly greater in oblique than pure lateral impacts at the mid and lower thoracic levels. These response data are valuable in oblique lateral impact assessments.     

Integrated approach to PCE‐impacted site characterization,site management,and enhanced bioremediation

Tetrachloroethene (PCE)‐ and trichloroethene (TCE)‐impacted sites pose significant challenges even when site characterization activities indicate that biodegradation has occurred naturally. Although site‐specific, regulatory, and economic factors play roles in the remedy‐selection process, the application of molecular biological tools to the bioremediation field has streamlined the assessment of remedial alternatives and allowed for detailed evaluation of the chosen remedial technology. The case study described here was performed at a PCE‐impacted site at which reductive dechlorination of PCE and TCE had led to accumulation of cis‐dichlorethene (cis‐DCE) with concentrations ranging from approximately 10 to 100 mg/L. Bio‐Trap® samplers and quantitative polymerase chain reaction (qPCR) enumeration of Dehalococcoides spp. were used to evaluate three remedial options: monitored natural attenuation, biostimulation with HRC®, and biostimulation with HRC‐S®. Dehalococcoides populations in HRC‐S‐amended Bio‐Traps deployed in impacted wells were on the order of 10³ to 10⁴ cells/bead but were below detection limits in most unamended and HRC‐amended Bio‐Traps. Thus the in situ Bio‐Trap study identified biostimulation with HRC‐S as the recommended approach, which was further evaluated with a pilot study. After the pilot HRC‐S injection, Dehalococcoides populations increased to 10⁶ to 10⁷ cells/bead, and concentrations of cis‐DCE and vinyl chloride decreased with concurrent ethene production. Based on these results, a full‐scale HRC‐S injection was designed and implemented at the site. As with the pilot study, full‐scale HRC‐S injection promoted growth of Dehalococcoides spp. and stimulated reductive dechlorination of the daughter products cis‐DCE and vinyl chloride. © 2008 Wiley Periodicals, Inc.     

Phosphorus and nitrogen sorption to soils in the presence of poultry litter-derived dissolved organic matter

Two environmental aspects associated with land application of poultry litter that have not been comprehensively evaluated are (i) the competition of dissolved organic matter (DOM) and P for soil sorption sites, and (ii) the sorption of dissolved organic nitrogen (DON) relative to inorganic nitrogen species (e.g., NO(3)(-) and NH(4)(+)) and dissolved organic carbon (DOC). The competition between DOM and P for sorption sites has often been assumed to increase the amount of P available for plant growth; however, elevating DOM concentrations may also increase P available for transport to water resources. Batch sorption experiments were conducted to (i) evaluate soil properties governing P sorption to benchmark soils of Southwestern Missouri, (ii) elucidate the impact of poultry litter-derived DOM on P sorption, and (iii) investigate DON retention relative to inorganic N species and DOC. Soils were reacted for 24 h with inorganic P (0-60 mg L(-1)) in the presence and absence of DOM (145 mg C L(-1)) using a background electrolyte solution comparable to DOM extracts (I = 10.8 mmol L(-1); pH 7.7). Soil P sorption was positively correlated with metal oxide (r(2) = 0.70) and clay content (r(2) = 0.79) and negatively correlated with Bray-1 extractable P (r(2) = 0.79). Poultry litter-derived DOM had no significant negative impact on P sorption. Dissolved organic nitrogen was preferentially removed from solution relative to (NO(3)(-)-N + NO(2)(-)-N), NH(4)(+)-N, and DOC. This research indicates that poultry litter-derived DOM is not likely to enhance inorganic P transport which contradicts the assumption that DOM released from organic wastes increases plant-available P when organic amendments and fertilizer P are co-applied. Additionally, this work demonstrates the need to further evaluate the fate and transport of DON in agroecosystem soils receiving poultry litter applications.     

Characterization of Semi-refined Carrageenan-Based Film for Primary Food Packaging Purposes

Carrageenan-based films demonstrate good performance, the raw materials for their production are abundant in nature and can be sustainably sourced from seaweeds. Similar to other naturally-derived biopolymers, however, carrageenans are relatively expensive to purify and form into useful materials. In order to potentially lower the production costs compared to pure carrageenan, semi-refined carrageenan (SRC) plasticized with 0–50% (w/w) glycerol was investigated using a solution casting method. The film color and opacity increased along with the moisture content, whereas the water vapor permeability decreased with increasing levels of glycerol. The tensile properties of the SRC films improved significantly, particularly at glycerol additions greater than 30% (w/w). Moreover, the addition of glycerol improved the thermal stability and altered the surface morphology of the films. In general, the properties of the SRC films were comparable with refined carrageenan films suggesting that SRC has potential to be furthered developed into more cost effective primary food packaging materials.     

Late Holocene wetland transgression and 500 years of vegetation and fire variability in the semi-arid Amboseli landscape,southern Kenya

The semi-arid Amboseli landscape, southern Kenya, is characterised by intermittent groundwater-fed wetlands that form sedimentary geoarchives recording past ecosystem changes. We present a 5000-year environmental history of a radiocarbon dated sediment core from Esambu Swamp adjacent to Amboseli National Park. Although radiocarbon dates suggest an unconformity or sedimentary gap that spans between 3800 and 500 cal year BP, the record provides a unique insight into the long-term ecosystem history and wetland processes, particularly the past 500 years. Climatic shifts, fire activity and recent anthropogenic activity drive changes in ecosystem composition. Prior to 3800 cal year BP the pollen data suggest semi-arid savanna ecosystem persisted near the wetland. The wetland transgressed at some time between 3800 and 500 cal year BP and it is difficult to constrain this timing further, and palustrine peaty sediments have accumulated since 400 cal year BP. Increased abundance of Afromontane forest taxa from adjacent highlands of Kilimanjaro and the Chyulu Hills and local arboreal taxa reflect changes in regional moisture budgets. Particularly transformative changes occurred in the last five centuries, associated with increased local biomass burning coeval with the arrival of Maa-speaking pastoralists and intensification of the ivory trade. Cereal crops occurred consistently from around 300 cal year BP, indicative of further anthropogenic activity. The study provides unique insight in Amboseli ecosystem history and the link between ecosystem drivers of change. Such long-term perspectives are crucial for future climate change and associated livelihood impacts, so that suitable responses to ensure sustainable management practices can be developed in an important conservation landscape.