Electrocatalytic reduction of nitrate ions from water using polyaniline nanofibers modified gold electrode

Polyaniline (PANI) nanofibers were electrochemically synthesized on gold electrode using ethanol as soft template by the cyclic voltammetry technique. The PANI nanofibers were characterized by Fourier transform infrared spectroscopy, UV-visible spectroscopy, and scanning electron microscopy. Linear sweep voltammetry was used to investigate electrocatalytic activity of the PANI nanofibers modified electrode toward the reduction of nitrate ions. Results showed that the electroreduction process strongly depends on the applied potential. At the potential value of about -0.8 V vs Ag/AgCl, the electroreduction of nitrate anions to nitrite anions was identified as the rate-determining step of the electroreduction process. In the potential range of -0.8 to -1.0 V, reduction of nitrite to hydroxylamine occurs, followed by the reduction to ammonia. At potentials more negative than -1.0 V, nitrite is directly reduced to ammonia. This study demonstrates the effectiveness of PANI nanofibers modified electrode in the electroreduction of nitrate ions compared to traditional reduction methods.     

Resolving the interactions between population density and air pollution emissions controls in the San Joaquin Valley, USA

The effectiveness of emissions control programs designed to reduce concentrations of airborne particulate matter with an aerodynamic diameter < 2.5 microm (PM2.5) in California's San Joaquin Valley was studied in the year 2030 under three growth scenarios: low, medium, and high population density. Base-case inventories for each choice of population density were created using a coupled emissions modeling system that simultaneously considered interactions between land use and transportation, area source, and point source emissions. The ambient PM2.5 response to each combination of population density and emissions control was evaluated using a regional chemical transport model over a 3-week winter stagnation episode. Comparisons between scenarios were based on regional average and population-weighted PM2.5 concentrations. In the absence of any emissions control program, population-weighted concentrations of PM2.5 in the future San Joaquin Valley are lowest undergrowth scenarios that emphasize low population density. A complete ban on wood burning and a 90% reduction in emissions from food cooking operations and diesel engines must occur before medium- to high-density growth scenarios result in lower population-weighted concentrations of PM2.5. These trends partly reflect the fact that existing downtown urban cores that naturally act as anchor points for new high-density growth in the San Joaquin Valley are located close to major transportation corridors for goods movement. Adding growth buffers around transportation corridors had little impact in the current analysis, since the 8-km resolution of the chemical transport model already provided an artificial buffer around major emissions sources. Assuming that future emissions controls will greatly reduce or eliminate emissions from residential wood burning, food cooking, and diesel engines, the 2030 growth scenario using "as-planned" (medium) population density achieves the lowest population-weighted average PM2.5 concentration in the future San Joaquin Valley during a severe winter stagnation event. Implications: The San Joaquin Valley is one of the most heavily polluted air basins in the United States that are projected to experience strong population growth in the coming decades. The best plan to improve air quality in the region combines medium- or high-density population growth with rigorous emissions controls. In the absences of controls, high-density growth leads to increased population exposure to PM2.5 compared with low-density growth scenarios (urban sprawl).     

Determination of partition and diffusion coefficients of formaldehyde in selected building materials and impact of relative humidity

The partition and effective diffusion coefficients of formaldehyde were measured for three materials (conventional gypsum wallboard, "green" gypsum wallboard, and "green" carpet) under three relative humidity (RH) conditions (20%, 50%, and 70% RH). The "green" materials contained recycled materials and were friendly to environment. A dynamic dual-chamber test method was used. Results showed that a higher relative humidity led to a larger effective diffusion coefficient for two kinds of wallboards and carpet. The carpet was also found to be very permeable resulting in an effective diffusion coefficient at the same order of magnitude with the formaldehyde diffusion coefficient in air. The partition coefficient (K(ma)) of formaldehyde in conventional wallboard was 1.52 times larger at 50% RH than at 20% RH, whereas it decreased slightly from 50% to 70% RH, presumably due to the combined effects of water solubility of formaldehyde and micro-pore blocking by condensed moisture at the high RH level. The partition coefficient of formaldehyde increased slightly with the increase of relative humidity in "green" wallboard and "green" carpet. At the same relative humidity level, the "green" wallboard had larger partition coefficient and effective diffusion coefficient than the conventional wallboard, presumably due to the micro-pore structure differences between the two materials. The data generated could be used to assess the sorption effects of formaldehyde on building materials and to evaluate its impact on the formaldehyde concentration in buildings.     

Assessment of a regulatory model's performance relative to large spatial heterogeneity in observed ozone in Houston, Texas

In Houston, some of the highest measured 8-hr ozone (O3) peaks are characterized by sudden increases in observed concentrations of at least 40 ppb in 1 hr or 60 ppb in 2 hr. Measurements show that these large hourly changes appear at only a few monitors and span a narrow geographic area, suggesting a spatially heterogeneous field of O3 concentrations. This study assessed whether a regulatory air quality model (AQM) can simulate this observed behavior. The AQM did not reproduce the magnitude or location of some of the highest observed hourly O3 changes, and it also failed to capture the limited spatial extent. On days with measured large hourly changes in O3 concentrations, the AQM predicted high O3 over large regions of Houston, resulting in overpredictions at several monitors. This analysis shows that the model can make high O3, but on these days the predicted spatial field suggests that the model had a different cause. Some observed large hourly changes in O3 concentrations have been linked to random releases of industrial volatile organic compounds (VOCs). In the AQM emission inventory, there are several emission events when an industrial point source increases VOC emissions in excess of 10,000 mol/hr. One instance increased predicted downwind O3 concentrations up to 25 ppb. These results show that the modeling system is responsive to a large VOC release, but the timing and location of the release, and meteorological conditions, are critical requirements. Attainment of the O3 standard requires the use of observational data and AQM predictions. If the large observed hourly changes are indicative of a separate cause of high O3, then the model may not include that cause, which might result in regulators enacting control strategies that could be ineffective.     

Ambient nitrogen oxides exposure and early childhood respiratory illnesses

Acute respiratory infections are common in children below 5 years and recent studies suggest a possible link with air pollution. In this study, we investigated the association between ambient nitrogen oxides (NO_x) and bronchitis or upper airway inflammation.This longitudinal study was conducted in Teplice and Prachatice districts, Czech Republic. Children were followed from birth to 4.5 years of age. Data were compiled from medical records at delivery and at follow up, and from self-administered questionnaires from the same two time points. Air pollution monitoring data were used to estimate exposure over five different averaging periods ranging from three to 45 days prior to an episode. To quantify the association between exposure and outcome, while accounting for repeated measure correlation we conducted logistic regression analysis using generalized estimating equations.During the first 2 years of life, the adjusted rate ratio for bronchitis associated with interquartile increase in the 30-day average NO_x was 1.31 [95% confidence interval (CI): 1.07, 1.61] and for two to 4.5 year olds, it was 1.23 (95% CI: 1.01, 1.49). The 14-day exposure also had stable association across both age groups: below 2 years it was 1.25 (95% CI: 1.06, 1.47) and for two to 4.5 years it was 1.21 (95% CI: 1.06, 1.39). The association between bronchitis and NO_x increased with child's age in the under 2 years group, which is a relatively novel finding.The results demonstrate an association between NO_x and respiratory infections that are sufficiently severe to come to medical attention. The evidence, if causal, can be of public health concern because acute respiratory illnesses are common in preschool children.     

Contribution of sociodemographic characteristics, occupation, diet and lifestyle to DDT and DDE concentrations in serum and adipose tissue from a Bolivian cohort

The organochlorine pesticide p,p′-Dichlorodiphenyltrichloroethane (DDT) was widely used in the early 1960s-70s for vector control in tropical and subtropical areas of South America. Due to its persistence, DDT has a high potential to bioaccumulate in the food chain and living organisms and is a major public health concern, especially in South America.The main purpose of the present study was to investigate predictors of serum and adipose tissue concentrations of p,p′-DDT and its main metabolite, p,p′-dichlorodiphenyldichloroethylene (p,p′-DDE), in an adult cohort (n = 112) from Santa Cruz de la Sierra, Bolivia, using multiple linear regression models. These models explained 29.3-47.8% of the variability in adipose tissue concentrations of p,p′-DDT and p,p′-DDE, respectively, and 32.9-47.0% of that in serum. Main exposure predictors included age, occupational class, residence, diet, smoking habit, and accumulated breastfeeding time.This is one of the few studies to explore predictors of human exposure to these chemicals using a multivariate approach in a South American population. Results show that predictors of human exposure to p,p′-DDT and p,p′-DDE in Santa Cruz de la Sierra may diverge from those found in other populations of the world, due to particular sociodemographic and lifestyle characteristics of this region.     

Nutrient leaching in a Colombian savanna Oxisol amended with biochar

Nutrient leaching in highly weathered tropical soils often poses a challenge for crop production. We investigated the effects of applying 20 t ha biochar (BC) to a Colombian savanna Oxisol on soil hydrology and nutrient leaching in field experiments. Measurements were made over the third and fourth years after a single BC application. Nutrient contents in the soil solution were measured under one maize and one soybean crop each year that were routinely fertilized with mineral fertilizers. Leaching by unsaturated water flux was calculated using soil solution sampled with suction cup lysimeters and water flux estimates generated by the model HYDRUS 1-D. No significant difference ( > 0.05) was observed in surface-saturated hydraulic conductivity or soil water retention curves, resulting in no relevant changes in water percolation after BC additions in the studied soils. However, due to differences in soil solution concentrations, leaching of inorganic N, Ca, Mg, and K measured up to a depth of 0.6 m increased ( < 0.05), whereas P leaching decreased, and leaching of all nutrients (except P) at a depth of 1.2 m was significantly reduced with BC application. Changes in leaching at 2.0 m depth with BC additions were about one order of magnitude lower than at other depths, except for P. Biochar applications increased soil solution concentrations and downward movement of nutrients in the root zone and decreased leaching of Ca, Mg, and Sr at 1.2 m, possibly by a combination of retention and crop nutrient uptake.     

H(+)/phenanthrene symporter and aquaglyceroporin are implicated in phenanthrene uptake by wheat (Triticum aestivum L.) roots

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous organic pollutants that are toxic to human and nonhuman organisms. Dietary intake of PAHs is a dominant route of exposure for the general population because food crops are a major source of dietary PAHs. The mechanism for crop root uptake of PAHs remains unclear. Here we reveal that wheat root uptake of PAHs involves active and passive processes. The passive uptake is mercury and glycerol dependent. Mercury and glycerol inhibit uptake, indicating that aquaglyceroporins sensitive to mercury contribute to passive uptake. Active uptake is mediated by a phenanthrene/H symporter. The electrical response of wheat roots triggered by phenanthrene consists of two sequential phases: depolarization followed by repolarization. The depolarization is phenanthrene concentration dependent, with saturation kinetics that have an apparent of K(m) 10.8 μmol L(-1). As uptake proceeds, external solution pH increase is noticed. Lower pH favors the uptake. Vanadate and 2,4-dinitrophenol suppress the electrical response to phenanthrene and phenanthrene uptake, suggesting that plasma membrane H(+)-ATPase is involved in the establishment of an electrochemical proton gradient acting as a driving force for active uptake. Therefore, it is suggested that aquaglyceroporin and phenanthrene/H symporter are implicated in phenanthrene uptake. Our results provide insight into PAH uptake mechanism in wheat roots that is relevant to strategies for reducing PAH accumulation in wheat for food safety, improving phytoremediation of PAH-contaminated soils or water by agronomic practices and genetic modification to target remedial plants for higher PAH uptake capacity.     

The Tarland Catchment Initiative and its effect on stream water quality and macroinvertebrate indices

The Tarland Catchment Initiative is a partnership venture between researchers, land managers, regulators, and the local community. Its aims are to improve water quality, promote biodiversity, and increase awareness of catchment management. In this study, the effects of buffer strip installations and remediation of a large septic tank effluent were appraised by water physico-chemistry (suspended solids, NO, NH, soluble reactive P) and stream macroinvertebrate indices used by the Scottish Environmental Protection Agency. It was done during before and after interventions over an 8-yr period using a paired catchment approach. Because macroinvertebrate indices were previously shown to respond negatively to suspended solid concentrations in the study area, the installation of buffer strips along the headwaters was expected to improve macroinvertebrate scores. Although water quality (soluble reactive P, NH) improved downstream of the septic tank effluent after remediation, there was no detectable change in macroinvertebrate scores. Buffer strip installations in the headwaters had no measurable effects (beyond possible weak trends) on water quality or macroinvertebrate scores. Either the buffer strips have so far been ineffective or ineffectiveness of assessment methods and sampling frequency and time lags in recovery prevent us detecting reliable effects. To explain and appreciate these constraints on measuring stream recovery, continuous capacity building with land managers and other stakeholders is essential; otherwise, the feasibility of undertaking sufficient management interventions is likely to be compromised and projects deemed unsuccessful.     

Effects of riparian forest buffers on in-stream nutrient retention in agricultural catchments

In northeastern Austria, marshlands have been turned into the most productive arable land of the country. As a result, most headwater streams show structurally degraded channels, lacking riparian buffer zones, which are heavily loaded with nutrients from the surrounding crop fields. The present study examines whether longitudinally restricted riparian forest buffers can enhance the in-stream nutrient retention in nutrient-enriched headwater streams. We estimated nutrient uptake from pairwise, short-term addition experiments with NH, NH, PO, and NaCl within reaches with riparian forest buffers (RFB) and degraded reaches (DEG) of the same streams. Riparian forest buffers originated from the conservation of the pristine vegetation or from restoration measures. Hydrologic retention was calculated with the model OTIS-P on the basis of conductivity break-through curves from the salt injections. A significant increase in surface transient storage was revealed in pristine and restored RFB reaches compared with DEG reaches due to the longitudinal step-pool pattern and the frequent occurrence of woody debris on the channel bed. Ammonium uptake lengths were significantly shorter in RFB reaches than in DEG reaches, resulting from the higher hydrologic retention. Uptake velocities did not differ significantly between RFB and DEG reaches, indicating that riparian forest buffers did not affect the biochemical nutrient demand. Uptake of NH was mainly driven by autotrophs. Net PO uptake was not affected by riparian forest buffers. The study shows that the physical and biogeochemical effects of riparian forest buffers on the in-stream nutrient retention are limited in the case of highly eutrophic streams.