Seasonal and diurnal measurements of carbon monoxide and nonmethane hydrocarbons at Mt. Wilson,California: Indirect evidence of atomic Cl in the Los Angeles basin

We present a study of the seasonal and diurnal variability of carbon monoxide and selected volatile organic compounds in the Los Angeles area. Measurements were made during four different nine-day field campaigns in April/May, September, and November, 2007, and February, 2008, at the Mt. Wilson sampling site, which is located at an elevation of approximately 1700 m in the San Gabriel Mountains overlooking Pasadena and the Los Angeles basin. The results were used to characterize the Mt. Wilson site as a representative location for monitoring integrated Los Angeles basin emissions, and, by reference to carbon monoxide emissions, to estimate average annual emissions. The considerable seasonal variability of many hydrocarbons, in both their measured mixing ratios and their relationship to carbon monoxide, was indicative of variable source strengths. Most interestingly, perturbation of C₄ hydrocarbon ratios suggested an enhanced role for chlorine chemistry during the month of September, likely as the result of Los Angeles’ coastal location. Such coastal influence was confirmed by observations of enhanced mixing ratios of marine halocarbons, as well as air mass back trajectories.     

How to Constrain Multi‐Objective Calibrations of the SWAT Model Using Water Balance Components

Accurate discharge simulation is one of the most common objectives of hydrological modeling studies. However, a good simulation of discharge is not necessarily the result of a realistic simulation of hydrological processes within the catchment. We propose an evaluation framework that considers both discharge and water balance components as evaluation criteria for calibration of the Soil and Water Assessment Tool (SWAT). In this study, we integrated average annual values of surface runoff, groundwater flow, and evapotranspiration in the model evaluation procedure to constrain the selection of good model runs for the Little River Experimental Watershed in Georgia, United States. For evaluating water balance and discharge dynamics, the Nash‐Sutcliffe efficiency (NSE) and percent bias (PBIAS) were used. In addition, the ratio of root mean square error and standard deviation of measured data (RSR) was calculated for individual segments of the flow duration curve to identify the best model runs in terms of discharge magnitude. Our results indicate that good statistics for discharge do not guarantee realistic simulations of individual water balance components. Therefore, we recommend constraining the ranges of water balance components to achieve a more realistic simulation of the entire hydrological system, even if tradeoffs between good statistics for discharge simulations and reasonable amounts of the water balance components are unavoidable. Editor's note : This paper is part of the featured series on SWAT Applications for Emerging Hydrologic and Water Quality Challenges. See the February 2017 issue for the introduction and background to the series.     

Removal of heavy metal ions from wastewaters using dendrimer-functionalized multi-walled carbon nanotubes

Dendrimer-functionalized multi-walled carbon nanotubes (MWCNT) for heavy metal ion removal from wastewaters were developed. Triazole dendrimers (TD) were built directly onto the carbon nanotube surface by successive click chemistry reactions affording the zero- and first-generation dendrimer-functionalized MWCNT (MWCNT-TD1 and MWCNT-TD2). The Moedritzer-Irani reaction carried out on the amino groups present on the MWCNT-TD2 sample gave the corresponding α-aminophosphonate nanosystem MWCNT-TD2P. Both MWCNT-TD2 and MWCNT-TD2P nanosystems have been characterized by physical, chemical, and morphological analyses. Their chelating abilities towards the toxic metal ions Pb²⁺, Hg²⁺, and Ni²⁺ and the harmless Ca²⁺ ion have been experimentally evaluated in the two different sets of experiments and at the salt concentrations of 1 mg/mL or 1 μg/mL by inductively coupled plasma mass spectrometry (ICP-MS). The results of these studies pointed out the interesting chelating behavior for the phosphonated nanosystem towards the Hg²⁺ ion. The complexation mode of the best chelating system MWCNT-TD2P with mercury was investigated through density functional theory (DFT) calculations, suggesting a chelation mechanism involving the two oxygen atoms of the phosphate group. The synthesized dendrimers, supported on the multi-walled carbon nanotubes, have shown the potential to be used for the selective toxic metal ion removal and recovery.     

Inputs and distributions of synthetic musk fragrances in an estuarine and coastal environment; a case study

Synthetic musks are ubiquitous contaminants in the environment. Compartmental distributions (dissolved, suspended particle associated and sedimentary) of the compounds throughout an axial estuarine transect and in coastal waters are reported. High concentrations of Galaxolide^® (HHCB) and Tonalide^® (AHTN) (987-2098 ng/L and 55-159 ng/L, respectively) were encountered in final effluent samples from sewage treatment plants (STPs) discharging into the Tamar and Plym Estuaries (UK), with lower concentrations of Celestolide^® (ADBI) (4-13 ng/L), Phantolide^® (AHMI) (6-9 ng/L), musk xylene (MX) (4-7 ng/L) and musk ketone (MK) (18-30 ng/L). Rapid dilution from the outfalls is demonstrated with resulting concentrations of HHCB spanning from 5 to 30 ng/L and those for AHTN from 3 to 15 ng/L. The other musks were generally not detected in the estuarine and coastal waters. The suspended particulate matter (SPM) and sedimentary profiles and compositions (HHCB:AHTN ratios) generally reflect the distribution in the water column with highest concentrations adjacent to sewage outfalls.     

Growth responses of crop and weed species to heavy metals in pot and field experiments

Greenhouse and field studies were performed to examine the growth responses and possible phytoremediation capacity towards heavy metals of several Brassicaceae (Brassica alba, Brassica carinata, Brassica napus and Brassica nigra) and Poaceae (durum wheat and barley). Soils used featured total concentrations of Cr, Cu, Pb and Zn largely exceeding the maximum levels permitted by the Italian laws. Different organic amendments were tested such as a compost and the plant growth-promoting rhizobacterium Bacillus licheniformis. In the greenhouse experiment, plant length, leaf area index and shoots dry matter were evaluated periodically for the Brassicaceae examined. Whereas plant length, grains production, weight of 1,000 seeds, ear fertility and tiller density were determined under field conditions at the end of the crop cycle for wheat and barley. In general, the species tested appeared to be tolerant to high heavy metal concentrations in soil, and slightly significant differences were found for all parameters considered. A marked growth increase was shown to occur for Brassicaceae cultivated on compost- and bacillus-amended contaminated soils, with respect to non-amended contaminated soils. With some exception, higher growth parameters were measured for wheat and barley plants cropped from contaminated soils in comparison to non-contaminated soils. Further, bacillus amendment enhanced the length of wheat and barley plants in both non-contaminated and contaminated soils, while different effects were observed for the other parameters evaluated.     

A validated 2-D diffusion–advection model for prediction of drift from ground boom sprayers

Correct field drift prediction is a key element in environmental risk assessment of spraying applications. A reduced order drift prediction model based on the diffusion–advection equation is presented. It allows fast assessment of the drift potential of specific ground boom applications under specific environmental wind conditions that obey the logarithmic wind profile. The model was calibrated based on simulations with a validated Computational Fluid Dynamics (CFD) model. Validation of both models against 38 carefully conducted field experiments is successfully performed for distances up to 20 m from the field edge, for spraying on flat pasture land. The reduced order model succeeded in correct drift predictions for different nozzle types, wind velocities, boom heights and spray pressures. It used 4 parameters representing the physical aspects of the drift cloud; the height of the cloud at the field edge, the mass flux crossing the field edge, the settling velocity of the droplets and the turbulence. For the parameter set and range considered, it is demonstrated for the first time that the effect of the droplet diameter distribution of the different nozzle types on the amount of deposition spray drift can be evaluated by a single parameter, i.e., the volume fraction of droplets with a diameter smaller than 191 μm. The reduced order model can be solved more than 4 orders of magnitude faster than the comprehensive CFD model.