Airborne measurements of peroxy radicals using the PERCA technique

The Peroxy Radical Chemical Amplifier (PERCA) technique is a proven method for measurement of ambient levels of peroxy radicals at ground level, but there are no published instances of the technique being used on an aerial platform. Here we describe deployment of a PERCA on the former UK Meteorological Office C-130 Hercules research aircraft. The instrument uses the established method of chemical amplification and conversion of peroxy radicals to nitrogen dioxide (NO2) by doping the sample air-flow matrix with CO and NO, subsequently measuring the NO2 yield with an improved 'Luminox' LMA-3 NO2 detector. NO2 from the amplification chemistry is distinguished from other sources of NO2 reaching the detector by periodically injecting CO approximately 1 s downstream of the NO injection point (termination mode). Chain lengths (CL's) for the amplification chemistry were typically approximately 260 (ground level) to approximately 200 (7,000 m). This variation with altitude is less than the variation associated with the 'age' of the PFA inlet material where the amplification chemistry occurs; CL's of approximately 200 with old tubing to approximately 300 with new clean tubing were typical (ground level values). The CL determinations were made in-flight using an onboard calibration unit based on the 254 nm photolysis of 7.5 to 10 parts per billion (by volume, ppbv) of CH3I in air, producing CH3O2 in a quantitative manner. The noise-equivalent detection limit for peroxy radicals (HO2 + RO2) is 2 parts per trillion (by volume, pptv) at 3,650 m when the background ambient ozone levels are stable, based on a 5 min average of five 30 s amplification cycles and five 30 s termination cycles. This detection limit is a function of several factors but is most seriously degraded when there is large variability in the ambient ozone concentration. This paper describes the instrument design, considers its performance and proposes design improvements. It concludes that the performance of an airborne PERCA in the free troposphere can be superior to that of ground-based instruments when similar sampling frequencies are compared.     

Solubilization of manganese and trace metals in soils affected by acid mine runoff

Manganese solubility has become a primary concern in the soils and water supplies in the Alamosa River basin, Colorado due to both crop toxicity problems and concentrations that exceed water quality standards. Some of the land in this region has received inputs of acid and trace metals as a result of irrigation with water affected by acid mine drainage and naturally occurring acid mineral seeps. The release of Mn, Zn, Ni, and Cu following saturation with water was studied in four soils from the Alamosa River basin. Redox potentials decreased to values adequate for dissolution of Mn oxides within 24 h following saturation. Soluble Mn concentrations were increased to levels exceeding water quality standards within 84 h. Soluble concentrations of Zn and Ni correlated positively with Mn following reduction for all four soils studied. The correlation between Cu and Mn was significant for only one of the soils studied. The soluble concentrations of Zn and Ni were greater than predicted based on the content of each of these metals in the Mn oxide fraction only. Increases in total electrolyte concentration during reduction indicate that this may be the result of displacement of exchangeable metals by Mn following reductive dissolution of Mn oxides.     

Maternal investment in sons and daughters: problems of methodology

Summary The prediction that mothers should invest more in sons than daughters was briefly examined in American bison (Bison bison) by Wolff (1988). He concluded that (a) male calves suckle more than females, (b) cows that had previously produced sons were more likely to be barren, and (c) cows that had male calves became estrous later in the year than other cows. In this paper we present data from two long term studies at different sites to show that Wolff's conclusions are equivocal at best and difficult to reconcile with predictions of the hypothesis because of questionable methods and assumptions. Offprint requests to: W.C.H. Green     

Evaluation of wind fields used in Grand Canyon Visibility Transport Commission analyses

The Grand Canyon Visibility Transport Commission (GCVTC) was established by the U.S. Congress to assess the potential impacts of projected growth on atmospheric visibility at Grand Canyon National Park and to make recommendations to the U.S. Environmental Protection Agency on what measures could be taken to avoid such adverse impacts. A critical input to the assessment tool used by the commission was three-dimensional model-derived wind fields used to transport the emissions. This paper describes the evaluation of the wind fields used at various stages in the assessment. Wind fields evaluated included those obtained from the Colorado State University Regional Atmospheric Modeling System (RAMS), the National Meteorological Center's Nested Grid Model (NGM), and the National Oceanic and Atmospheric Administration's Atmospheric Transport and Dispersion (ATAD) trajectory model. The model-derived wind fields were evaluated at multiple vertical levels at several locations in the southwestern United States by determining differences between model predicted winds and winds that were measured using radiosonde and radar wind profiler data. Model-derived winds were also evaluated by determining the percent of time that they were within acceptable differences from measured winds. All models had difficulties, generally meeting the acceptable criteria for less than 50% of the predictions. The RAMS model had a persistent bias toward southwesterly winds at the expense of other directions, especially failing to represent channeling by north-south mountain ranges in the lower levels. The NGM model exhibited a substantial bias in the summer months by extending northwesterly winds in the eastern Pacific Ocean well inland, in contrast to the observed southwesterlies at inland locations. The simpler ATAD trajectory model performed somewhat better than the other models, probably because of its use of more upper air sites. The results of the evaluation indicated that these wind fields could not be used to reliably predict source-receptor impacts on a particular day; thus, seasonally averaged impacts were used in the GCVTC assessment.     

Treatment of phenol wastewater by microwave-induced CIO_2-CuO_x/Al_2O_3 catalytic oxidation process

The catalyst of CuO_x/Al_2O_3 was prepared by the dipping-sedimentation method usingγ-Al_2O_3 as a supporter.CuO and Cu_2O were loaded on the surface of Al_2O_3,characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS).In the presence of CuO_x/Al_2O_3,the microwave-induced chlorine dioxide(ClO_2) catalytic oxidation process was conducted for the treatment of synthetic wastewater containing 100 mg/L phenol.The factors influencing phenol removal were investigated and the results showed that microwave-induced ClO_2-CuO_x/Al_2O_3 process could effectively degrade contaminants in a short reaction time with a low oxidant dosage,extensive pH range.Under a given condition(ClO_2 concentration 80 mg/L,microwave power 50 W,contact time 5 min,catalyst dosage 50 g/L,pH 9),phenol removal percentage approached 92.24%,corresponding to 79.13% of COD_(Cr) removal.The removal of phenol by microwave-induced ClO_2-CuO_x/Al_2O_3 catalytic oxidation process was a complicated non-homogeneous solid/water reaction, which fitted pseudo-first-order by kinetics.Compared with traditional ClO_2 oxidation,ClO_2 catalytic oxidation and microwave-induced ClO_2 oxidation,microwave-induced ClO_2 catalytic oxidation system could significantly enhance the degradation efficiency.It provides an effective technology for the removal of phenol wastewater.     

Linking field experiments to long-term simulation of impacts of nitrogen deposition on heathlands and moorlands

The results from three long-term field manipulation studies of the impacts of increased nitrogen deposition (0–120 kg N ha^–1 yr^–1) on lowland and upland heathlands in the UK were compared, to test if common responses are observed. Consistent increases in Calluna foliar N content and decreases in litter C:N ratios were found across all sites, while increases in N leaching were not observed at any site over the range 0–80 kg ha^–1 yr^–1. However, the response of Calluna biomass did vary between sites, possibly reflecting site differences in nutrient status and management histories. Five versions of a simulation model of heathland responses to N were developed, each reflecting different assumptions about the fate and turnover of soil N. Model outputs supported the deduction from mass balance calculations at two of the field sites that N additions have resulted in an increase in immobilisation; the latter was needed to prevent the model overestimating measured N leaching. However, this version of the model significantly underestimated Calluna biomass. Model versions, which included uptake of organic N by Callunaand re-mobilisation of N from the soil organic store provided some improvement in the fit between modelled and field biomass data, but re-mobilisation also led to an overestimation of N leaching. Quantification of these processes and their response to increased N deposition are therefore critical to interpreting experimental data and predicting the long-term impacts of atmospheric deposition on heathlands and moorlands.     

Discharge From the Edwards Aquifer Through the Leona River Floodplain,Uvalde, Texas1

Abstract: Analysis of results from an electrical resistivity survey, a magnetic survey, and an aquifer test performed on the Leona River floodplain in south‐central Texas indicates that ground‐water discharge from the Edwards Aquifer through the Leona River floodplain may be as great as 91.7 Mm³/year. When combined with an estimate of 8.8 Mm³/year for surface flow in the Leona River, as much as 100.5 Mm³/year could be discharged from the Edwards Aquifer through the Leona River floodplain. A value of 11,200 acre‐ft/year (13.82 Mm³/year) has been used as the calibration target in existing ground‐water models for total discharge from Leona Springs and the Leona River. Including ground water or underflow discharge would significantly increase the calibration target in future models. This refinement would improve the conceptualization of ground‐water flow in the western portion of the San Antonio segment of the Edwards Aquifer and would thereby allow for more accurate assessment and management of the ground‐water resources provided by the Edwards Aquifer.