Response of atmospheric deposition and surface water chemistry to the COVID-19 lockdown in an alpine area.

The effects of the COVID-19 lockdown on deposition and surface water chemistry were investigated in an area south of the Alps. Long-term data provided by the monitoring networks revealed that the deposition of sulfur and nitrogen compounds in this area has stabilized since around 2010; in 2020, however, both concentrations and deposition were significantly below the average values of the previous decade for SO4 and NO3. Less evident changes were observed for NH4 and base cation. The estimated decrease of deposition in 2020 with respect to the previous decade was on average - 54% and - 46% for SO4 and NO3, respectively. The lower deposition of SO4 and NO3 recorded in 2020 was caused by the sharp decrease of SO2 and particularly of NOx air concentrations mainly due to the mobility restrictions consequent to the COVID-19 lockdown. The limited effects on NH4 deposition can be explained by the fact that NH3 emission was not affected by the lockdown, being mainly related to agricultural activities. A widespread response to the decreased deposition of S and N compounds was observed in a group of pristine freshwater sites, with NO3 concentrations in 2020 clearly below the long-term average. The rapid chemical recovery observed at freshwater sites in response to the sharp decrease of deposition put in evidence the high resilience potential of freshwater ecosystems in pristine regions and demonstrated the great potential of emission reduction policy in producing further substantial ameliorations of the water quality at sensitive sites.

Glacier Melting Increases the Solute Concentrations of Himalayan Glacial Lakes.

Over the past two decades, we observed a substantial rise in ionic content that was mainly determined by the sulfate concentration at 20 remote high elevation lakes located in central southern Himalaya. At LCN9, which was monitored on an annual basis for the last 20 years, the sulfate concentrations increased over 4-fold. Among the main causes, we exclude a change in the composition of wet atmospheric deposition, as well as a possible influence of decrease in seasonal snow cover duration, which could have exposed larger basin surfaces to alteration processes. Glacier retreat likely was the main factor responsible for the observed increase of sulfate concentrations. We attribute this chemical changes mainly to the sulfide oxidation processes that occur in subglacial environments. Moreover, we observe that the weakened monsoon of the past two decades has only partially contributed to the lakes enrichment through runoff waters that are more concentrated in solutes or lowering the water table, resulting in more rock exposed to air and enhanced mineral oxidation.

Influence of QA/QC procedures on non-sampling error in deposition monitoring in forests.

A Working Ring Test (WRT) was organised in the framework of the EU Regulation (EC) No 2152/2003 ("Forest Focus") and of the UN/ECE Program "ICP Forests" to evaluate the overall performance of the laboratories monitoring atmospheric deposition and soil solution in European Forests. Seven natural samples of atmospheric deposition and soil solutions and 5 synthetic solutions were distributed to 52 laboratories, which analysed them using their routine methods. Thirteen variables are considered in this paper: pH, conductivity, calcium, magnesium, sodium, potassium, ammonium, sulfate, nitrate, chloride, total alkalinity, total dissolved nitrogen and dissolved organic carbon. For each variable, the relative standard deviation of the results was evaluated, after outlier rejection, to estimate the analytical error of the measurements. The results are evaluated considering the Quality Assurance/Quality Control (QA/QC) procedure included in the ICP Forests monitoring manual: consistency check of the data and use of control charts and internal standards. A Data Quality Objective (DQO) is defined for each of the variables and the number of data meeting the DQOs are discussed in relation to the QA/QC procedures adopted. Although 38% of the results did not meet the DQO, the laboratories adopting QA/QC procedures produced a larger proportion of results meeting the objective and a consistent part of the outliers could be detected a posteriori checking analyses consistence.

Determination of total dissolved inorganic carbon in freshwaters by reagent-free ion chromatography.

Studies of inorganic carbon cycle in natural waters provide important information on the biological productivity and buffer capacity. Determination of total inorganic carbon, alkalinity and dissolved carbon dioxide gives an indication of the balance between photosynthesis and respiration by biota, both within the water column and sediments, and carbon dioxide transfers from the water column to the atmosphere. There are few methods to measure and distinguish the different forms of inorganic carbon, but all require a measure or an indirect quantification of total inorganic carbon. A direct measurement of TIC in water is made possible by the introduction of electrolytic generated hydroxide eluent in ion chromatography which allows to detect a chromatographic peak for carbonate. The advantage of this method is that all the inorganic forms of carbon are converted in carbonate at eluent pH and can be detected as a single peak by conductivity detection. Repeatability of carbonate peak was evaluated at different levels from 0.02 to 6 mequiv.l(-1) both in high purity water and in real samples and ranged from 1 to 9%. The calibration curve was not linear and has to be fitted by a quadratic curve. Limit of detection was estimated to be 0.02 mequiv.l(-1). Accuracy has been estimated by comparing ion chromatography method with total inorganic carbon calculated from alkalinity and pH. The correlation between the two methods was good (R(2)=0.978, n=141). The IC method has been applied to different typologies of surface waters (alpine and subalpine lakes and rivers) characterised by different chemical characteristics (alkalinity from 0.05 to 2 mequiv.l(-1) and pH from 6.7 to 8.5) and low total organic carbon concentrations. This analytical method allowed to describe the distribution of TIC along the water column of two Italian deep lakes.