Iron-catalyzed oxidation of s(IV) species by oxygen in aqueous solution: Influence of pH on the redox cycling of iron

Redox cycling of Fe(II)/Fe(III) during the catalyzed aqueous S(IV) oxidation by dissolved oxygen in the presence of Fe(II) and/or Fe(III) at an initial pH_i of 4.4, often observed in atmospheric waters, was studied in detail. It has been found that the reaction rate is not considerably affected by the oxidation state of iron at the start of the reaction. An equilibrium between Fe(II) and Fe(III) was established a few minutes after the start of the reaction, regardless of the oxidation state of iron at the beginning of the experiment. The prevailing oxidation state of iron in a particular phase of the reaction depends on the concentration of S(IV) in the reaction solution. It has been found that the formation of polymerized hydroxo Fe(III) species is also included in the mechanism of the Fe-catalyzed oxidation of S(IV). The formation of these species was confirmed by the on-line measurement of Fe(II) and Fe_reac. The results also clearly demonstrate that the pH_i of the solution is a major factor, controlling the concentration of Fe(III) ions, the form of S(IV) species, and consequently the reaction rate of S(IV) oxidation by oxygen.     

Dynamics of phosphorus and phytate-utilizing bacteria during aerobic degradation of dairy cattle dung

During organic wastes degradation, P is transformed which may affect its availability. In this study, the dynamics of P and the occurrence of phytate-utilizing bacteria (PUB) were evaluated during aerobic degradation of dairy cattle dung in laboratory-scale reactors for 105 d. The results showed an increase of water-soluble inorganic P (Pi) (from 570 to 1890 mg kg(-1)) and biomass P (from 390 to 870 mg kg(-1)) during the initial 40 d. After this period, water-soluble Pi remained constant (around 1500 mg kg(-1)) and biomass P decreased (around 220 mg kg(-1)) probably due to the decrease of easily available C in dung. Under the acidic conditions in the first 20 d there was an increase in concentration of Al (25 mg kg(-1)) and Fe (27 mg kg(-1)) ions. These ions were no longer detectable in the alkaline conditions occurring after 40 d. In the same period, the Ca concentration increased (from 1170 to 2370 mg kg(-1)) and chemical speciation revealed permanent association of Ca ions with Pi. Sequential P fractionation showed a decrease of organic P in NaHCO(3), NaOH and HCl fractions and an increase of residual P (25-52% with respect to total P). Analysis by (31)P NMR also showed a decrease (from 14% to 1.6%) of phytic acid content during final experimental period (60 and 105 d). The bacteriological analysis revealed various PUB involved in degradation of the dung. Two morphotypes, genetically characterized as Enterobacter and Rahnella, which were dominant under higher content of residual P, showed strong utilization of phytate in vitro.     

Carbon monoxide concentrations in Santiago City at street levels and their vertical gradient

Carbon monoxide concentrations were measured at ground level (1 m) near heavy traffic streets in downtown Santiago de Chile in periods of low (November and December), intermediate (April) and high (May) ambient concentrations. Also, measurements were carried out at several heights (from 1 to 127 m) in Santiago’s main street during winter time. Measurements carried out at ground level show maximum values during the morning rush hour, with values considerably higher than those reported by the urban air quality network, particularly in summer time. However, the measured values are below air quality standards. Vertical CO profiles were measured in a tower located in the center of downtown. Below 40 m (average altitude of neighboring buildings), the profiles do not show a consistent vertical gradient, with CO concentrations increasing or decreasing with height, regardless of atmospheric stability. In this low altitude range, the observed vertical profiles are poorly predicted by a street canyon model, and the measured concentrations can not be described by a simple exponential decay. At higher altitudes (40 and 127 m) a negative gradient in CO concentrations is observed, both for stable and unstable atmospheric conditions. The values of CO measured at 127 m are relatively well described by an Eulerian dispersion model running with current CO emission inventories for Santiago, although this model tends to predict stepper CO gradients than the observed ones.     

Source apportionment of PM10 and PM(2.5) at Tocopilla, Chile (22 degrees 05' S, 70 degrees 12' W)

Tocopilla is located on the coast of Northern Chile, within an arid region that extends from 30 degrees S to the border with Perú. The major industrial activities are related to the copper mining industry. A measurement campaign was conducted during March and April 2006 to determine ambient PM10 and PM(2.5) concentrations in the city. The results showed significantly higher PM10 concentrations in the southern part of the city (117 microg/m3) compared with 79 and 80 (microg/m3) in the central and northern sites. By contrast, ambient PM2.5 concentrations had a more uniform spatial distribution across the city, around 20 (microg/m3). In order to conduct a source apportionment, daily PM10 and PM(2.5) samples were analyzed for elements by XRF. EPA's Positive Matrix Factorization software was used to interpret the results of the chemical compositions. The major source contributing to PM(2.5) at sites 1, 2 and 3, respectively are: (a) sulfates, with approximately 50% of PM2.5 concentrations at the three sites; (b) fugitive emissions from fertilizer storage and handling, with 16%, 21% and 10%; (c) Coal and residual oil combustion, with 15%, 15% and 4%; (d) Sea salt, 5%, 6% and 16%; (e) Copper ore processing, 4%, 5% and 15%; and (f) a mixed dust source with 11%, 7% and 4%. Results for PM10--at sites 1, 2 and 3, respectively--show that the major contributors are: (a) sea salt source with 36%, 32% and 36% of the PM10 concentration; (b) copper processing emissions mixed with airborne soil dust with 6.6%, 11.5% and 41%; (c) sulfates with 31%, 31% and 12%; (d) a mixed dust source with 16%, 12% and 10%, and (e) the fertilizer stockpile emissions, with 11%, 14% and 2% of the PM10 concentration. The high natural background of PM10 implies that major reductions in anthropogenic emissions of PM10 and SO2 would be required to attain ambient air quality standards for PM10; those reductions would curb down ambient PM(2.5) concentrations as well.     

Sedimentation rate of settleable particulate matter in Santiago city,Chile

Settleable particulate matter (SPM) is an atmospheric pollutant harmful to human health and the environment in high concentrations. Despite this fact, no up‐to‐date information on SPM levels exists for the capital of Chile, Santiago (7 million inhabitants). To address this knowledge gap, SPM sedimentation rates, including soluble and insoluble components, were measured at three different urban sites from July to November of 2016. We compare the measurements with ambient and meteorological information, as well as urban typology settings. Our results indicate SPM deposition rates between 2.5 and 3.9 g/(m²·30 days). Only one site exceeded the national limit of 4.5 g/(m²·30 days), but we found an increasing trend in all three sites. SPM and its insoluble sedimentation rates increased during warm and dry months and presented significant correlations with meteorological parameters. The highest sedimentation rates were measured at the location with the least permeable surfaces and the lowest green spaces, while the lowest sedimentation rates were found in the sites with abundant green spaces and permeable soil. No significant differences were detected in the soluble components. Our results suggest that SPM levels in Santiago are close to the national limit and may increase with climate change and urban expansion.