Trends in the content of acidifying and eutrophying compounds in atmospheric precipitation in an urbanized area

The trends in changing the content of sulfur and nitrogen in atmospheric precipitation in the territory of Minsk over an 18-year period are characterized on the basis of the analysis of the monitoring results of the chemical composition of atmospheric precipitation at the experimental site. A downtrend in the sulfur and nitrogen content combined with an uptrend in the precipitation acidity was identified. An average decrease (trend) in the content of sulfur in atmospheric precipitation for 2002–2019 was 0.019 mg S/dm3/year, of oxidized nitrogen – 0.008 mg/dm3, of reduced nitrogen – 0.019 mg/dm3. Over an 18-year period, the changes in the content of sulfur and nitrogen in atmospheric precipitation decreased the deposition of sulfur on average by 31.3 kg/km2/year, of oxidized nitrogen – by 15.4 kg/km2/year, of reduced nitrogen – by 25.6 kg/km2/year. It is shown that for the period from 2005 to 2012, the acidification potential of the natural environment decreased parallel to the reduction of the sulfur and nitrogen deposition; in the subsequent period, the trend of the acidification potential basically follows the trend of the precipitation of the main cations. It is revealed that the rates of average reduction in the content of oxidized sulfur and oxidized nitrogen in atmospheric precipitation in Minsk for the period from 2002 to 2017 are comparable to the rates of reduction of these compounds at the stations of the EMEP Program in Europe, and exceed those for reduced nitrogen.

Global modeling of cloud water acidity, precipitation acidity, and acid inputs to ecosystems

Cloud water acidity affects the atmospheric chemistry of sulfate and organic aerosol formation, halogen radical cycling, and trace metal speciation. Precipitation acidity including post-depositional inputs adversely affects soil and freshwater ecosystems. Here, we use the GEOS-Chem model of atmospheric chemistry to simulate the global distributions of cloud water and precipitation acidity as well as the total acid inputs to ecosystems from wet deposition. The model accounts for strong acids (H2SO4, HNO3, and HCl), weak acids (HCOOH, CH3COOH, CO2, and SO2), and weak bases (NH3 as well as dust and sea salt aerosol alkalinity). We compile a global data set of cloud water pH measurements for comparison with the model. The global mean observed cloud water pH is 5.2±0.9, compared to 5.0±0.8 in the model, with a range from 3 to 8 depending on the region. The lowest values are over East Asia, and the highest values are over deserts. Cloud water pH over East Asia is low because of large acid inputs (H2SO4 and HNO3), despite NH3 and dust neutralizing 70 % of these inputs. Cloud water pH is typically 4–5 over the US and Europe. Carboxylic acids account for less than 25 % of cloud water H+ in the Northern Hemisphere on an annual basis but 25 %–50 % in the Southern Hemisphere and over 50 % in the southern tropical continents, where they push the cloud water pH below 4.5. Anthropogenic emissions of SO2 and NOx (precursors of H2SO4 and HNO3) are decreasing at northern midlatitudes, but the effect on cloud water pH is strongly buffered by NH4+ and carboxylic acids. The global mean precipitation pH is 5.5 in GEOS-Chem, which is higher than the cloud water pH because of dilution and below-cloud scavenging of NH3 and dust. GEOS-Chem successfully reproduces the annual mean precipitation pH observations in North America, Europe, and eastern Asia. Carboxylic acids, which are undetected in routine observations due to biodegradation, lower the annual mean precipitation pH in these areas by 0.2 units. The acid wet deposition flux to terrestrial ecosystems taking into account the acidifying potential of NO3- and NH4+ in N-saturated ecosystems exceeds 50 meqm-2a-1 in East Asia and the Americas, which would affect sensitive ecosystems. NH4+ is the dominant acidifying species in wet deposition, contributing 41 % of the global acid flux to continents under N-saturated conditions.

Separation and Qualitative Analysis of Carbonate, Phosphate and Chromate Anions in Qualitative Inorganic Courses

In the present work, our experience with a new methodology for separation and characterization of carbonate, phosphate and chromate anions is discussed. Since 2014 this laboratory experiment has been applied in undergraduate Chemistry courses in University of Lavras, Brazil, has shown to be satisfactory along Qualitative Inorganic or Analytical courses. In order to understand and to discuss the experiment, concepts involving equilibria of precipitation, acidity and basicity, liquid-liquid extraction, as well as the notions of solubility, phases distribution of solutes, and distribution diagram of the species were explored.

Long-term air concentrations, wet deposition, and scavenging ratios of inorganic ions, HNO₃, and SO₂ and assessment of aerosol and precipitation acidity at Canadian rural locations

This study analyzed long-term air concentrations and annual wet deposition of inorganic ions and aerosol and precipitation acidity at 31 Canadian sites from 1983 to 2011. Scavenging ratios of inorganic ions and relative contributions of particulate- and gas-phase species to NH4+, NO3−, and SO42− wet deposition were determined. Geographical patterns of atmospheric Ca2+, Na+, Cl−, NH4+, NO3−, and SO42− were similar to wet deposition and attributed to anthropogenic sources, sea-salt emissions, and agricultural emissions. Decreasing trends in atmospheric NH4+ (1994–2010) and SO42− (1983–2010) were prevalent. Atmospheric NO3− increased prior to 2001 and then declined afterwards. These results are consistent with SO2, NOx and NH3 emission trends in Canada and the USA. Widespread declines in annual NO3− and SO42− wet deposition ranged from 0.07 to 1.0 kg ha−1 a−1 (1984–2011). Acidic aerosols and precipitation impacted southern and eastern Canada more than western Canada; however, both trends have been decreasing since 1994. Scavenging ratios of particulate NH4+, SO42− and NO3− differed from literature values by 22 %, 44 %, and a factor of 6, respectively, because of the exclusion of gas scavenging in previous studies. Average gas and particle scavenging contributions to total wet deposition were estimated to be 72 % for HNO3 and 28 % for particulate NO3−, 37 % for SO2 and 63 % for particulate SO42−, and 30 % for NH3 and 70 % for particulate NH4+.

Long-term air concentrations, wet deposition, and scavenging ratios of inorganic ions, HNO₃ and SO₂ and assessment of aerosol and precipitation acidity at Canadian rural locations

This study analyzed long-term air concentrations and annual wet deposition of inorganic ions and aerosol and precipitation acidity at 30 Canadian sites from 1983–2011. Scavenging ratios of inorganic ions and relative contributions of particulate- and gas-phase species to NH4+, NO3−, and SO42− wet deposition were determined. Long-term median atmospheric NH4+, NO3−, and SO42− between sites ranged from 0.1–1.7, 0.03–2.0, and 0.6–3.5 μg m−3, respectively. Their median annual wet deposition varied from 0.2–5.8, 0.8–23.3, and 0.8–26.6 kg ha−1 a−1. Geographical patterns of atmospheric Ca2+, Na+, Cl−, NH4+, NO3−, and SO42− were similar to wet deposition and attributed to anthropogenic sources, sea-salt emissions, and agricultural emissions. Decreasing trends in atmospheric NH4+ (1994–2010) and SO42− (1983–2010) were prevalent. Atmospheric NO3− increased from 1991–2001 and declined from 2001–2010. These results are consistent with SO2, NOx and NH3 emission trends in Canada and the U.S. Widespread declines in annual NO3− and SO42− wet deposition ranged from 0.07–1.0 kg ha−1 a−1 (1984–2011). Acidic aerosols and precipitation impacted southern and eastern Canada more than western Canada; however both trends have been decreasing since 1994. Scavenging ratios of particulate NH4+, SO42− and NO3− differed from literature values by 22 %, 44 % and a factor of 6, respectively, because of the exclusion of gas scavenging. Average gas and particle scavenging contributions to wet NO3− deposition were 72±23 % for HNO3 and 28±23 % for particulate NO3−. SO2 and particulate SO42− contributed 37±20 % and 63±20 % to wet SO42− deposition, respectively. NH3 and particulate NH4+ contributed 30±19 % and 70±19 % to wet NH4+ deposition.