Influence of Catchment Characteristics and Flood Type on Relationship Between Streamwater Chemistry and Streamflow: Case Study from Carpathian Foothills in Poland

The study aimed to determine the influence of catchment characteristics and flood type on the relationship between streamflow and a number of chemical characteristics of streamwater. These were specific electrical conductivity (SC), pH, the concentrations of main ions (Ca²⁺, Mg²⁺, Na⁺, K⁺, HCO ₃ ^? , SO ₄ ^2? , and Cl^?), and nutrients (NH ₄ ⁺ , NO ₂ ^? , NO ₃ ^? , and PO ₄ ^3? ). These relationships were studied in three small catchments with different geological structure and land use. Several flood types were distinguished based on the factors that initiate flooding and specific conditions during events. Geological factors led to a lower SC and main ion concentrations at a given specific runoff in catchments built of resistant sandstone versus those built of less resistant sediments. A lower concentration of nutrients was detected in the semi-natural woodland catchment versus agricultural and mixed-use catchments, which are strongly impacted by human activity. The strongest correlation between streamflow and the chemical characteristics of water was found in the woodland catchment. Different types of floods were characterized by different ion concentrations. In the woodland catchment, higher SC and higher concentrations of most main ions were noted during storm-induced floods than during floods induced by prolonged rainfall. The opposite was true for the agricultural and mixed-use catchments. During snowmelt floods, SC, NO ₃ ^? , and most main ion concentrations were higher when the soil was unfrozen in the agricultural and mixed-use catchments versus when the soil was frozen. In the case of the remaining nutrients, lower concentrations of NH ₄ ⁺ were detected during rain-induced floods than during snowmelt floods. The opposite was true of PO ₄ ^3? .     

Mid-term trends in acid precipitation,streamwater chemistry and element budgets in the strengbach catchment (Vosges Mountains,France)

In the Vosges Mountains (NE of France), integrated plot-catchment studies have been carried out since 1985 in the Strengbach basin to study the influence of acid atmospheric inputs on surface water quality and element budgets. In this paper, available mid-term time series (1985–1991) have been considered to detect obvious trends, if any, in surface water chemistry and element budgets. Air quality data showed a slight decline for SO₂, whereas NO₂ slightly increased over the period, but these trends are not very significant. This is in agreement with increased N concentration (mainly as NH ₄ ⁺ ) and with the stability of SO ₄ ^2? in open field precipitation. Because of a significant decrease in rainfall amount over the period, only inputs of NH ₄ ⁺ increased significantly whereas H⁺ and SO ₄ ²⁺ inputs declined. In spring and streamwaters, pH and dissolved Si concentration increased mainly as a result of a reduced flow. Na⁺, K⁺, Cl^? and HCO-3~^? concentrations remained stable whereas Ca²⁺, Mg²⁺ and SO ₄ ²⁺ concentrations declined significantly. Only NO ₃ ^? concentration increased significantly in springwaters. The catchment budgets revealed significant losses of base cations, Si and SO ₄ ^2? . These losses decreased over the period. Nitrogen was retained in the ecosystem. However, a longer record is needed to determine whether or not changes in surface water chemistry have resulted from short-term flow reductions or long-term changes in input-output ion budgets. This is specially true with N because the decline in SO ₄ ^2? output was accompanied by N accumulation.     

Simulating acidification and recovery processes in experimental catchments with the ILWAS model

The Integrated Lake Watershed Acidification Study (ILWAS) model was used to simulate soil discharge chemistry at two neighboring experimental catchments. One catchment underwent deacidification because of the artificial application of deacidified precipitation whereas the other catchment received unaltered acidic precipitation. Simulated results reproduce the observed seasonal dynamics in the concentrations of base cations, NO ₃ ^? , Al, and H₄SiO ₄ ⁰ in soil discharges for both catchments. Simulated results also indicate that the export flux of base cations was decreased by 30% at the deacidification catchment in response to the decrease in acid deposition. However, simulated SO ₄ ^2? concentrations show decreases that are about 40% more rapid than were observed. Simulated organic acid concentrations were also substantially lower than those observed at the deacidification catchment, indicating that organic matter decomposition processes were not correctly simulated. Acid-base budgets for both 5 and 50-yr simulations indicate that acid displacement by base cations through ion exchange is the principal process delaying recovery of runoff alkalinity, whereas SO ₄ ^2? desorption has a minor role. Silicate weathering is the dominant acid-consuming process at both catchments. Criteria proposed here for assessing forecast reliability include reproducing seasonal dynamics in discharge chemistry, providing numerically accurate chemical concentrations when compared to monitoring data, and correctly predicting deacidification rate and extent. The ILWAS model generally meets these criteria, indicating that the model can produce a reliable forecast of the effects of acid deposition on the acid-base chemistry of surface waters given sufficient temporal data for confident optimization of the calibrated variables in the model.     

Deposition of nutrients and major ions by precipitation in south-central Ontario

As part of a study of the substance budgets of lakes in south-central Ontario, a network of precipitation collectors (8 bulk, 7 wet only) was operated to measure the deposition of nutrients and major ions. Results are reported for total P, total Kjeldahl N, NO ₃ ^? ?N, NH ₄ ⁺ ?N, total N, Fe, H⁺, Ca⁺⁺, Mg⁺⁺, Na⁺, K⁺, SO ₄ ⁼ and CL^? for a two year period (August 1976–July 1978). On an equivalent basis the dominant anion in both bulk and wet precipitation was SO ₄ ⁼ , with H⁺ the dominant cation. Precipitation in the study area is more acidic than that analyzed at any other location on the Canadian Shield to date. Concentrations of ions varied by 1 to 3 orders of magnitude between individual precipitation events and annual deposition varied by as much as 2-fold in the two years of study. Annual wet deposition contributed >60% of bulk deposition for all substances except total P. Seasonal trends in deposition with summer maxima were noted for most ions. For Harp Lake, a small Precambrian Lake with a lake area of 12.6% of its total drainage area, precipitation input directly to the lake surface was an important source of nutrients and major ions. This was especially the case for P, N and H⁺ because these substances were retained by the terrestrial drainage basin.     

Biotic and abiotic processes controlling water chemistry during snowmelt at rabbit ears pass,Rocky Mountains,Colorado, U.S.A.

The chemical composition of snowmelt, groundwater, and streamwater was monitored during the spring of 1991 and 1992 in a 200-ha subalpine catchment on the western flank of the Rocky Mountains near Steamboat Springs, Colorado. Most of the snowmelt occurred during a one-month period annually that began in mid-May 1991 and mid-April 1992. The average water quality characteristics of individual sampling sites (meltwater, streamwater, and groundwater) were similar in 1991 and 1992. The major ions in meltwater were differentially eluted from the snowpack, and meltwater was dominated by Ca²⁺, SO ₄ ^2? , and NO ₃ ^? . Groundwater and streamwater were dominated by weathering products, including Ca²⁺, HCO ₃ ^? (measured as alkalinity), and SiO₂, and their concentrations decreased as snowmelt progressed. One well had extremely high NO ₃ ^? . concentrations, which were balanced by Ca²⁺ concentrations. For this well, hydrogen ion was hypothesized to be generated from nitrification in overlying soils, and subsequently exchanged with other cations, particularly Ca²⁺. Solute concentrations in streamwater also decreased as snowmelt progressed. Variations in groundwater levels and solute concentrations indicate that most of the meltwater traveled through the surficial materials. A mass balance for 1992 indicated that the watershed retained H⁺, NH ₄ ⁺ , NO ₃ ^? , SO ₄ ^2? and Cl^? and was the primary source of base cations and other weathering products. Proportionally more SO ₄ ^2? was deposited with the unusually high summer rainfall in 1992 compared to that released from snowmelt, whereas NO ₃ ^? was higher in snowmelt and Cl^? was the same. The sum of snowmelt and rainfall could account for greater than 90% of the H⁺ and NH ₄ ⁺ retained by the watershed and greater than 50% of the NO ₃ ^? .     

Deposition of air pollutants in a wind-exposed forest edge

The atmospheric deposition of air pollutants at a forest edge was studied by means of monitoring canopy throughfall at the edge and at five different parallel lines in the forest behind the edge. The investigation was carried out at a pine forest on the Swedish west coast. Throughfall and bulk deposition samples were analyzed for volume, SO ₄ ^2? , NO ₃ ^? , Cl^?, NH ₄ ⁺ , Na⁺, K⁺, Mg²⁺, Ca²⁺, and for pH. The results show that the throughfall flow at the edge was increased substantially for most ions. The ratios in throughfall flows between the edge and the line 50 m into the forest were for SO ₄ ^2? , 1.5, NO ₃ ^? 2.9, NH ₄ ⁺ 2.7, and Na⁺ 3.1. Since this effect is not only valid for forest edges but also for hillsides, hilltops, and edges between stands of different age, etc., there might be substantial areas which get much larger total deposition than the normally considered closed forest.     

Long-term development of element budgets in a Norway spruce (Picea abies (L.) Karst.) forest of the German solling area

To evaluate ecosystem response to changing atmospheric deposition, element budgets were established over the period from 1973 to 1991 for a Norway Spruce (Picea abies (L.) Karst.) site. Budgets for Na⁺, Cl^?, Ca²⁺, Mg²⁺, N, S and H⁺ were based on total deposition and seepage water fluxes. The deposition of Ca²⁺, Mg²⁺, particularly, of S and H⁺ decreased with time, while calculated N deposition remained constant at a high level. The decrease in Ca²⁺ deposition led to a reduction of Ca²⁺ fluxes with seepage water. The decrease of Mg²⁺ deposition did not have an effect on the output fluxes of Mg²⁺. The reversibility of soil and seepage water acidification by reduced S deposition was delayed by the release of previously accumulated soil SO ₄ ^2? . The highest NO ₃ ^? fluxes were observed during the period of 1986 to 1988; NO ₃ ^? fluxes in general demonstrated a considerable annual and periodic variation. Total N accumulation in the ecosystem amounted to nearly 590 kg ha^?1 yr^?1 during the observation period. The major sink of N in the spruce site is the aggrading humus layer. The results emphasize the need for measurements over several years to make conclusions regarding the function of ecosystems in response to atmospheric deposition.     

Stream chemistry impacts of conifer harvesting in welsh catchments

Hydrochemical data have been collected for between 6 and 9 years from forest harvesting experiments in small catchments (>10 ha) at Plynlimon and Beddgelert, Wales, UK. Felling resulted in rapid increases in NO ₃ ^? and K⁺ concentrations at both sites. A maximum of 3.2 mg N L^?1 was observed at Plynlimon about one year after the start of felling. Concentrations declined to control stream values (0.5 mg N L^?1) after 5 years. At Beddgelert, NO ₃ ^? concentrations in the manipulated catchments remained above those in the unfelled control catchment for three years, before declining below control values. The NO ₃ ^? pulse was related to increased rates of mineralization and nitrification in the soil after felling. The initial increase in K⁺ concentration after felling at Plynlimon was followed by a slow decline, but concentrations were still above those in the control stream after 5 years. From 4 to 8 years after felling at Beddgelert, K⁺ concentrations fell below and then generally remained lower than control values. The NO ₃ ^? pulse after felling at Plynlimon sustained inorganic anion concentrations above those in the control stream for the first 18 months after felling. As the NO ₃ ^? pulse declined, inorganic anion concentrations decreased to below those in the control stream about 4 years after felling. At Beddgelert, the smaller increase in NO ₃ ^? concentrations had less of an effect on inorganic anion concentrations which decreased after felling relative to values in the control stream. The increase in NO ₃ ^? was associated with temporary streamwater acidification in the felled catchments due to the increased rates of nitrification and nitrate leaching. At Plynlimon, streamwater filterable Al concentrations declined after felling, but controls on Al behaviour are complex and not explained by simple equilibrium relationships with Al(OH)₃ or by variations in inorganic anion concentrations. At Beddgelert, felling had no effect on stream water filterable Al concentrations. Felling at Plynlimon led to a large reduction in streamwater Cl^?, Na⁺ and SO ₄ ^2? concentrations. At Beddgelert reductions in SO ₄ ^2? and ‘sea salt’ ion concentrations were less clear, reflecting the smaller proportions of the catchments which were harvested. Felling had no deleterious effects on water quality, apart from a temporary slight further decline in stream pH at Beddgelert. Increases in NO ₃ ^? concentrations were short-lived and concentrations were well below drinking water standards. Filterable Al concentrations were already higher than statutory standards, but were not increased or decreased through felling.     

Nutrient Fluxes in Planted Norway Spruce Stands of Different Age in Southern Poland

The fluxes of N–NO ₃ ^? , N–NH ₄ ⁺ , S–SO ₄ ^2? , Na⁺, K⁺, Ca²⁺ and Mg²⁺ from bulk precipitation to throughfall, stemflow and soil water surface flows were studied during 1999–2003 in planted Norway spruce forest stands of different ages (11, 24, 91 and 116 years in 1999). Also, runoff from the corresponding Potok Dupniański Catchment in the Silesian Beskid Mts was studied. N deposition was above the critical load for coniferous trees. The interception increased with stand age as well as leaf area index and so did the leaching from the canopy of almost all the analysed elements, but especially S–SO ₄ ^2? , H⁺ and K⁺. The nutrient fluxes varied with age of the spruce stands. Throughfall showed a high amount of S and of the strong acids (S–SO ₄ ^2? and N–NO ₃ ^? ) deposited to the soil, especially in older spruce age classes. Decomposition of organic matter caused a rise in water acidity and an increase in the concentrations of all the analysed ions; the leaching of minerals, however, was low (under 1%). The horizontal soil water flow showed an increase in the amount of water and amount of ions and contributed to a further decrease of pH at the soil depth of 20 cm. Element concentrations and their amounts increased with water penetrating vertically and horizontally on the slopes. Considerable amounts of ions, especially S and alkaline cations, were carried beyond the reach of the root system and then left the catchment. In the long term, these mineral losses will adversely affect health and growth of the spruce stands, and the increased acidity with stand age will presumably have negative effects on the runoff water ecosystem.     

Examination of the Dissolved Inorganic Nitrogen Budget in Three Experimental Microbasins with Contrasting Land Cover—A Mass Balance Approach

A long-term hydrological and water chemistry research was conducted in three experimental microbasins differing in land cover: (1) a purely agricultural fertilized microbasin, (2) a forested microbasin dominated by Carpinus betulus (European hornbeam), and (3) a forested microbasin dominated by Picea abies (L.) (Norway spruce). The dissolved inorganic nitrogen (DIN: NH ₄ ⁺ , NO ₂ ^? , NO ₃ ^? ) budget was examined for a period of 3 years (1991–1993). Mean annual loads of DIN along with sulfate SO ₄ ^2? and base cations Ca²⁺, Mg²⁺, Na⁺, K⁺, and HCO ₃ ^? were calculated from ion concentrations measured in stream water, open-area rainfall, throughfall (under tree canopy), and streamwater at the outlets from the microbasins. Comparison of the net imported/exported loads showed that the amount of NO ₃ ^? leached from the agricultural microbasin is ～3.7 times higher (43.57 kg ha^?1?a^?1) than that from the spruce dominated microbasin (11.86 kg ha^?1?a^?1), which is a markedly higher export of NO ₃ ^? compared to the hornbeam dominated site. Our analyses showed that land cover (tree species) and land use practices (fertilization in agriculture) may actively affect the retention and export of nutrients from the microbasins, and have a pronounce impact on the quality of streamwater. Sulfate export exceeded atmospheric rainfall inputs (measured as wet deposition) in all three microbasins, suggesting an additional dry depositions of SO ₄ ^2? and geologic weathering.     

Long-term sulfate dynamics at lange bramke (Harz) used for testing two acidification models

At Lange Bramke (Harz) soil solution and runoff concentrations of major elements were observed over 16 yr. During this period acid deposition was high but showed a marked decrease of H⁺ and SO ₄ ^2? both in concentrations and fluxes over the last five years. Among others, this record reveals the following patterns: seasonality in the signals for SO ₄ ^2? and NO ₃ ^? in runoff which are synchronous; an accumulation of SO ₄ ^2? in the soil, initially up to 50% of the deposition fluxes; apparently no correlation between runoff and SO ₄ ^2? concentration, and no long-term trend in runoff concentration of SO ₄ ^2? . In this paper we use these patterns in the data set from Lange Bramke to test two established acidification models. The test criterion is that the algorithms employed by the SO ₄ ^2? modules of these models must be able to reproduce these features. To that end, both models need not to be run as it can be shown that even with completely unrestricted parameter values the two algorithms are unable to match the observed SO ₄ ^2? dynamics. The MAGIC model (Cosbyet al., 1985) is unable to reproduce, given the existence of net SO ₄ ^2? accumulation, the constant SO ₄ ^2? concentration in runoff during the last 16 years. The second model, BEM (Prenzel, 1986), is succesful in reconstructing the constant SC>4~ levels in runoff. However, on a monthly time scale BEM predicts a shift between the periodic maximum concentrations of SO ₄ ^2? and NO ₃ ^? which is not observed in the data.     

A method for evaluation of acidic sulfate and nitrate in precipitation

A simple method is presented and used to estimate the portions of SO _inf4 ^sup2? and NO _inf? ^sup3 that contribute to the strong acidity in weekly precipitation samples collected at three NADP sites in the eastern United States. The method assumes that, in general, the difference between SO _inf4 ^sup2? and NH _inf+ ^sup4 represents acidic sulfate and the difference between NO _inf? ^sup3 and soil-derived materials (the sum of Ca²⁺, Mg²⁺, and K⁺) represents acidic nitrate. Acidic sulfate and nitrate are considered to be the predominant source of H⁺ (determined from laboratory pH) in the weekly precipitation samples. Most of the acidity for all three sites was attributed to acidic sulfate. The highest fraction of acidic SO _inf4 ^sup2? to H⁺ wet deposition values was for the east-central Tennessee site (0.95) and the northeastern Illinois site (0.90), and the lowest fraction occurred at the central Pennsylvania site (0.75). The Tennessee site had the greatest acidic fraction of sulfate (0.84) and the Pennsylvania site had the greatest acidic fraction of nitrate (0.59).     

Sulfur and oxygen isotope ratios in sulfate during an acidification reversal study at Lake Gårdsjön,Western Sweden

The reversibility of acidification is being investigated in a full scale catchment manipulation experiment at Lake Gårdsjön on the Swedish west coast using isotopes as environmental tracers. A 6300 m² roof over the catchment enables researchers to control depositional variables. Stable S isotope values were determined in bulk deposition, throughfall, runoff, groundwater and soil-extracted water during one year prior to and two years of experimental control. Data collected prior to experimental control suggest that the inorganic SO ₄ ^2? pool within the catchment has a homogeneousδ ³⁴S value of about+5.5‰. Sprinkling of water spiked with small amounts of sea-water derived SO ₄ ^2? started in April 1991. Theδ ³⁴S value of this SO ₄ ^2? is around+19.5‰. Since April 1991, the SO ₄ ^2? concentration in runoff has decreased by some 30%, however, theδ ³⁴S value have increased by only 0.5‰. This suggests mixing of sprinkling water S with a large reservoir of S in the catchment. Oxygen isotopes in SO ₄ ^2? suggest that less than one third of the SO ₄ ^2? in runoff is secondary SO ₄ ^2? formed within the soil profile. This is, however, no evidence for net mineralization of S. The SO ₄ ^2? in runoff in the roofed catchment is a mixture of SO ₄ ^2? previously adsorbed in the soil, mineralized organic S and SO ₄ ^2? from the sprinkler water. Calculations based on isotope data indicate that the turnover time of S within the catchment is on the order of decades. Since SO ₄ ^2? facilitates base cation flow, the acidification reversal will take a much longer time than concentration decreases of SO ₄ ^2? would suggest.     

Effects of Land Use on Hydrochemistry and Contamination of Karst Groundwater from Nandong Underground River System, China

The Nandong Underground River System (NURS) is located in Southeast Yunnan Province, China. Groundwater in NURS plays a critical role in socio-economical development of the region. However, with the rapid increase of population in recent years, groundwater quality has degraded greatly. In this study, the analysis of 36 groundwater samples collected from springs in both rain and dry seasons shows significant spatial disparities and slight seasonal variations of major element concentrations in the groundwater. In addition, results from factor analysis indicate that NO ₃ ^? , Cl^?, SO ₄ ^2? , Na⁺, K⁺, and EC in the groundwater are mainly from the sources related to human activities while Ca²⁺, Mg²⁺, HCO ₃ ^? , and pH are primarily controlled by water–rock interactions in karst system with Ca²⁺ and HCO ₃ ^? somewhat from anthropogenic inputs. With the increased anthropogenic contaminations, the groundwater chemistry changes widely from Ca-HCO₃ or Ca (Mg)-HCO₃ type to Ca-Cl (+NO₃) or Ca (Mg)-Cl (+NO₃), and Ca-Cl (+NO₃+SO₄) or Ca (Mg)-Cl (+NO₃+SO₄) type. Concentrations of NO ₃ ^? , Cl^?, SO ₄ ^2? , Na⁺, and K⁺ generally show an indistinct grouping with respect to land use types, with very high concentrations observed in the groundwater from residential and agricultural areas. This suggests that those ions are mainly derived from sewage effluents and fertilizers. No specific land use control on the Mg²⁺ ion distribution is observed, suggesting Mg²⁺ is originated from natural dissolution of carbonate rocks. The distribution of Ca²⁺ and HCO ₃ ^? does not show any distinct land use control either, except for the samples from residential zones, suggesting the Ca²⁺ and HCO ₃ ^- mainly come from both natural dissolution of carbonate rocks and sewage effluents.     

Precipitation chemistry in Nova Scotia: 1978–1987

More than 1400 precipitation samples were collected weekly from 5 sites in Nova Scotia between 1978 and 1987. High concentrations of H⁺, non-marine SO _inf4 ^sup= (^*SO₄) and NO _inf3 ^sup- were observed in 1978 and 1986. In 1983, concentrations of all three parameters were the lowest in the data record. Fluctuations in emissions for SO₂ are insufficient to account for the variability observed in concentration and deposition values. Mean annual concentrations in 1983 were 13, 16, and 6 ueq L^-1 for H⁺, ^*SO₄, and NO _inf3 ^sup- , respectively. In 1986 the values were 35, 28, and 13 ueq L^-1. Concentrations in 1978 were 31, 38, and 16 ueq L^-1. Average pH of precipitation was 4.61 during the 10 yr study. The two most acidic years were 1979 (4.47) and 1986 (4.46). In 1983, the average pH was 4.89. The ratio (equivalents) of NO _inf3 ^sup- to ^*SO4 was 0.41, so most acidity in the precipitation results from H₂SO₄ However, multiple regression analysis revealed that H⁺ is more sensitive to changes in NO₃-concentrations than ^*SO₄. Ratios of summer (JJA) vs winter (JFM) average concentrations were examined. During summer months, ^*SO₄ and H⁺ were 1.8 times winter values. Summer to winter ratios for NO _inf3 ^sup- and NH _inf4 ^sup+ were 1.4 and 2.5, respectively.     

Nitrate reduction coupled with microbial oxidation of sulfide in river sediment

Purpose

Nitrate (NO ₃ ^? ) is often considered to be removed mainly through microbial respiratory denitrification coupled with carbon oxidation. Alternatively, NO ₃ ^? may be reduced by chemolithoautotrophic bacteria using sulfide as an electron donor. The aim of this study was to quantify the NO ₃ ^? reduction process with sulfide oxidation under different NO ₃ ^? input concentrations in river sediment.

Materials and methods

Under NO ₃ ^? input concentrations of 0.2 to 30?mM, flow-through reactors filled with river sediment from the Pearl River, China, were used to measure the processes of potential NO ₃ ^? reduction and sulfate (SO ₄ ^2? ) production. Molecular biology analyses were conducted to study the microbial mechanisms involved.

Results and discussion

Simultaneous NO₃ ^? removal and SO₄ ^2? production were observed with the different NO ₃ ^? concentrations in the sediment samples collected at different depths. Potentially, NO ₃ ^? removal reached 72 to 91?% and SO ₄ ^2? production rates ranged from 0.196 to 0.903?mM?h^?1. The potential NO ₃ ^? removal rates were linearly correlated to the NO ₃ ^? input concentrations. While the SO ₄ ^2? production process became stable, the NO ₃ ^? reduction process was still a first-order reaction within the range of NO ₃ ^? input concentrations. With low NO ₃ ^? input concentrations, the NO ₃ ^? removal was mainly through the pathway of dissimilatory NO ₃ ^? reduction to NH ₄ ⁺ , while with higher NO ₃ ^? concentrations the NO ₃ ^? removal was through the denitrification pathway.

Conclusions

While most of NO ₃ ^? in the sediment was reduced by denitrifying heterotrophs, sulfide-driven NO ₃ ^? reduction accounted for up to 26?% of the total NO ₃ ^? removal under lower NO ₃ ^? concentrations. The vertical distributions of NO ₃ ^? reduction and SO ₄ ^2? production processes were different because of the variable bacterial communities with depth.     

The geographical distribution and temporal variations of acidic deposition in Eastern North America

Data from two national precipitation chemistry monitoring networks, and several regional air and precipitation chemistry networks are used to describe some broad-scale features of acidic deposition in eastern North America. In northeastern North America, the coefficient of variation is shown to increase from 10–16% for annual averages to nearly 100% for daily values. There is a strong annual cycle in H⁺, SO _inf4 ^sup= and NH _inf4 ^sup+ deposition and some of the other ions although these cycles are not all in phase. The wet NO _inf3 ^sup? deposition contributes relatively more than SO _inf4 ^sup= to the acidity of snow as compared to rain. Wet deposition is highly “episodic” with about 50% to 70% of the total annual deposition of SO _inf4 ^sup= and NO _inf3 ^sup? accumulating in the highest 20% of the days. Estimates made in various ways indicate that, over eastern North America as a whole, dry deposition is approximately equal to wet for both SO _inf4 ^sup= and NO _inf3 ^sup? . Dry may exceed wet in the high emissions zone but drops to about 20% of the total deposition in more remote areas. Deposition via fog or low cloud impaction is an important input to high elevation forests, but more data are required to quantify the magnitude and regional extent of this.     

Intercomparison of snow Sampling and Analysis Within the Alpine-Wide Snowpack Investigation (SNOSP)

In order to investigate the seasonal and geographical distribution of snow concentrations anddeposition fluxes of environmentally relevant ionic species in the Alps, the international programSNOSP was initiated. In the framework of this program, intercomparisons of snow samplingtechniques and analytical methods to determine the ionic species C1^-, NO ₃ ^- ,SO ₄ ^2- , K⁺, Na⁺, NH4 ⁺, Mg²⁺, and Ca²⁺, as well as the pH and the specificconductivity were performed. The concentrations of these species in the snow samples collectedin the SNOSP program varied by orders of magnitude with, e.g., concentrations of NO ₃ ^- , SO ₄ ^2- , and NH4 ⁺ ranging from 0.2-60, 0.2-90, and 0.1-60 µeq L^-1,respectively. The intercomparisons revealed a reasonable agreement of the determinations of thespecies Cl^-, NO ₃ ^- , SO ₄ ^2- , Na⁺, and NH4 ⁺ in snow. Results were less satisfactory for K⁺, Mg²⁺, Ca²⁺,and H⁺, mainly due to the very low concentrations. In conclusion, recommendations areformulated for the reliable derivation of chemical inventories from snow packs.     

Simultaneous Removal of H2S, NH3, and Ethyl Mercaptan in Biotrickling Filters Packed with Poplar Wood and Polyurethane Foam: Impact of pH During Startup and Crossed Effects Evaluation

The present work discusses the startup and operation of different biotrickling filters during the simultaneous removal of NH₃, H₂S, and ethyl mercaptan (EM) for odor control, focusing on (a) the impact of pH control in the stability of the nitrification processes during reactor startup and (b) the crossed effects among selected pollutants and their by-products. Two biotrickling filters were packed with poplar wood chips (R1 and R2A), while a third reactor was packed with polyurethane foam (R2B). R2A and R2B presented a pH control system, whereas R1 did not. Loads of 2?C10?g N?CNH₃ m^?3?h^?1, 5?C16?g S?CH₂S m^?3?h^?1, and 1?C6?g EM m^?3?h^?1 were supplied to the bioreactors. The presence of a pH control loop in R2A and R2B proved to be crucial to avoid long startup periods and bioreactors malfunctioning due to biological activity inhibition. In addition, the impact of the presence of different concentrations of a series of N species (NH ₄ ⁺ , NO ₂ ^? , and NO ₃ ^? ) and S species (SO ₄ ^2? and S^2?) on the performance of the two biotrickling filters was studied by increasing their load to the reactors. Sulfide oxidation proved to be the most resilient process, since it was not affected in any of the experiments, while nitrification and EM removal were severely affected. In particular, the latter was affected by SO ₄ ^2? and NO ₂ ^? , while nitrification was significantly affected by NH ₄ ⁺ . The biotrickling filter packed with polyurethane foam was more sensitive to crossed effects than the biotrickling filter packed with poplar wood chips.     

Bulk Atmospheric Deposition in the Southern Po Valley (Northern Italy)

A study on pH and chemical composition of precipitation was carried out in two Italian sites, one urban (site 1) and one rural (site 2), located approximately 30 km far from Bologna, during a 3-year period. No significative site variation was found. In both locations, bulk deposition pH ranged from slightly acid to slightly alkaline, despite the volume weighted mean concentration of acidic species, NO ₃ ^? and SO ₄ ^2? (67.4 and 118.4 μeq l^?1 in site 1 and 88.7 and 103.8 μeq l^?1 in site 2), that were similar to those of typical acidic rainfall region. This might be ascribed to the neutralization reaction of the Ca²⁺, attributed to the calcareous soil and the frequent dusty air mass intrusion from the Sahara. The pair correlation matrix and the analysis of the main components suggested also ammonium and other crustal elements as neutralization agents. The depositional rate of SO ₄ ^2? and NO ₃ ^? , chemical elements of agricultural interest, amounted to 38 and 28 and 32 and 35 kg ha^?1 for site 1 and site 2, respectively. These supplies of nutrient were not negligible and had to be considered on cultivated lands. NH ₄ ⁺ deposition rate on site 2 was 7 kg ha^?1, 23% over site 1, probably due to nitrogen fertilization in the fields around the monitoring station. In site 1, SO ₄ ^2? presented a seasonal trend, indicating that its principal source was the residential heating. Results emphasized that the entity of the bulk deposition acidification is linked not only to the ions local emission sources (fossil fuel combustions, heating, and fertilizers) but also to the surrounding territory and the prevalent wind that transports through kilometers air masses which may contain acidic and alkaline species.