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.     

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.     

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.     

Ion mass budgets for small forested catchments in Finland

Ion mass and H⁺ budgets were calculated for three pristine forested catchments using bulk deposition, throughfall and runoff data. The catchments have different soil and forest type characteristics. A forest canopy filtering factor for each catchment was estimated for base cations, H⁺, Cl^? and SO ₄ ^2? by taking into account the specific filtering abilities of different stands based on the throughfall quality and the distribution of forest types. Output fluxes from the catchments were calculated from the quality and quantity of the runoff water. Deposition, weathering, ion exchange, retention and biological accumulation processes were taken into account to calculate catchment H⁺ budgets, and the ratio between external (anthropogenic) and internal H⁺ sources. In general, output exceeded input for Na⁺, K⁺, Ca²⁺, Mg²⁺, HCO ₃ ^? (if present) and A^? (organic anions), whereas retention was observed in the case of H⁺, NH ₄ ⁺ , NO ₃ ^? and SO ₄ ^2? . The range in the annual input of H⁺ was 22.8–26.3 meq m^?2 yr^?1, and in the annual output, 0.3–3.9 meq m^?2 yr^?1. Compared with some forested sites located in high acid deposition areas in southern Scandinavia, Scotland and Canada, the catchments receive rather moderate loads of acidic deposition. The consumption of H⁺ was dominated by base cation exchange plus weathering reactions (41–79 %), and by the retention of SO ₄ ^2? (17–49 %). The maximum net retention of SO ₄ ^2? was 87% in the HietajÄrvi 2 catchment, having the highest proportion of peatlands. Nitrogen transformations played a rather minor role in the H⁺ budgets. The ratio between external and internal H⁺ sources (excluding net base cation uptake by forests) varied between 0.74 and 2.62, depending on catchment characteristics and acidic deposition loads. The impact of the acidic deposition was most evident for the southern Valkeakotinen catchment, where the anthropogenic acidification has been documented also by palaeolimnological methods.     

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.     

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.     

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 ^? .     

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? .     

Mesoscale spatial variability of sulfate in air and rainwater at St. Louis

Sulfate concentrations in rainwater and in air measured on four summer days at St. Louis were highly variable, both spatially or temporally. Maximum/minimum ratios of aerosol SO _inf4 ^sup? varied by up to a factor of 9, and those in rainwater by a factor of 3 on the average. Generally, SO _inf4 ^sup? concentration patterns in air and rainwater were similar, and consistent with wind direction and the location of sources. Direct relationships between SO _inf4 ^sup? in air and in water were evident on two of the individual days, but not for all days together. The non-uniformity of the SO _inf4 ^sup? pattern plus consideration of possible sources of SO _inf4 ^sup? suggests that nucleation of SO _inf4 ^sup? particles must be a major cause of S scavenging, with some possible influence from sub-cloud impaction.     

Inorganic and organic sulfur profiles in nine Sphagnum peat bogs in the United States and Czechoslovakia

Depth profiles of total S, organic S, soluble SO ₄ ^2? -S, FeS, and FeS₂ were characterized for Sphagnum-derived peat cores collected from 9 sites. Marcell S-2 Bog (MN), Tamarack Swamp (PA), Cranesville Swamp (MD/WV), and Big Run Bog (WV) receive water from precipitation and upland runoff; atmospheric S deposition is 13, 47, 54, and 114 mmol m^?2, yr^?1, respectively. McDonald's Branch Swamp (NJ) is predominantly groundwater fed. Tub Run Bog (WV) and Allegheny Mining Bog (MD) receive augmented SO ₄ ^2? inputs through acid coal mine drainage. Jezerní slat' and Bo?í Dar Bog in Czechoslovakia receive atmospheric S inputs of 33 and 243 mmol m^?2 yr^?1, respectively. In the peat from all sites except Allegheny Mining Bog, where the substantially augmented SO ₄ ^2? input was reflected in an unusually high dissolved SO ₄ ^2? pool in the surface peat, organic S (probably mostly carbon bonded S) was the dominant S fraction; FeS₂ was generally the dominant inorganic S fraction. Subsurface peaks in total S, organic S and FeS₂-S in peat from the runoff water fed sites were interpreted as indicative of depth-dependent patterns in S reduction/oxidation and in S immobilization/mineralization. Unless SO ₄ ^2? inputs to a site are tremendously augmented (e.g., Allegheny Mining Bog), the rapid turnover of the dissolved SO ₄ ^2? pool combined with the relative stability of the other inorganic and organic S pools, apparently functions as an effective buffer against site differences in S inputs, leading to a general similarity in vertical S profiles in the peat deposits.     

Trends in surface water acidification at ecological monitoring sites in southeastern Canada (1981–1993)

Atmospheric deposition and surface water chemistry have been monitored intensively at 5 geologically “sensitive” sites in southeastern Canada. The sites receive differing acid inputs that span the entire range found in Canada. Surface water data collected at 9 stations from 1981 to 1993 for SO ₄ ^2? , NO ₃ ^? , Alkalinity, DOC, pH, Ca²⁺ and Mg²⁺ have been analyzed to detect monotonic trends. Similarities between the temporal patterns and trends for SO ₄ ^2? in deposition and surface water suggest that they are strongly linked at our sites. Our 13-year datasets showed significant negative SO ₄ ^2? trends at the 3 Ontario sites and a positive trend in Nova Scotia. A climatically-induced SO ₄ ^2? increase in northwestern Ontario has been reversed. Mobilization and export of adsorbed SO ₄ ^2? and/or reoxidized S from the basins of central Ontario sites is delaying their recovery. Two of our 9 stations (in Quebec and central Ontario) are continuing to acidify. The 2 Nova Scotia stations have the highest DOC levels and both exhibit a decreasing trend. Ionic compensation for declining SO ₄ ^2? varies from station to station, sometimes involving an Alk increase, sometimes a base cation decrease, and sometimes more complex combinations. Additional factors (e.g. climatic variation) also influence variable trends, and data records longer than those presently available will be needed to unequivocally verify acidification recovery.     

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.     

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.     

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).     

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.     

Difference in the Use of a Quartz Filter and a PTFE Filter as First-Stage Filter in the Four-Stage Filter-Pack Method

We evaluated the differences in the use of a quartz filter and a polytetrafluoroethylene (PTFE) filter as a first (F0)-stage filter in a four-stage filter-pack method. A four-stage filter-pack method can completely collect sulfur species (SO₂ and SO ₄ ^2? ), nitrate species (HNO₃ and NO ₃ ^? ), and ammonium species (NH₃ and NH ₄ ⁺ ) with little or no leakage irrespectively of the first-stage filter used. On the other hand, a seasonal variation was observed in the efficiency of collection between the quartz filter and the PTFE filter depending on the material to be collected. There was no seasonal variation in the efficiency of collection in sulfur species; in contrast, a clear seasonal variation was observed for the nitrate and ammonium species. As for NO ₃ ^? , the PTFE filter was more vulnerable than the quartz filter at air temperatures below 21°C, while the quartz filter was more vulnerable than the PTFE filter at air temperatures exceeding 21°C. A similar vulnerability for air temperature was observed for NH ₄ ⁺ , although the threshold air temperature was 23°C for NH ₄ ⁺ . Consequently, the evaporation loss of NO ₃ ^? would be mainly attributable to the volatilization of NH₄NO₃, although it is also partially due to the volatilization of NH₄Cl.     

Mercury antagonists: Effects of sodium chloride and sulfur group (VIa) compounds on excystment of the brine shrimp artemia

Brine shrimp excystment, although highly resistant, is severely inhibited by mmolar mercuric chloride. The presence of 100 mmolar NaCl largely prevents the toxic response. The chloride effect can be explained if the toxic Hg species, neutral HgCl₂, is converted into HgCl _inf3 ^sup2? and HgCl _inf4 ^sup2? since charged species not likely to penetrate cyst walls. Other Hg antagonists include SO _in3 ^su2? , SeO _inf3 ^sup2? , TeO _inf3 ^sup2? and TeO _inf4 ^sup2? , but not SO _inf4 ^sup2? and SeO _inf4 ^sup2? . The activity of both Te species can be explained by ready reduction of Te(VI) to Te(IV). Significant anti-mercurial effects were seen in mmolar thiols, ethionine and organoselenium compounds. Thiamine and methionine were both active Hg antagonists at 10 to 30 mmolar levels. The activities of S, Se and Cl^? compounds show that both geochemical and physiological modes of defense against and adaptation to high Hg levels exist.     

Throughfall quality and quantity in polluted and damaged ecosystems in Northern Bohemia

The interaction between high concentrations of polluting gases (SO₂ and NO_x) and damaged forest ecosystems was observed by studying throughfall precipitation in the Erzegebirge Mountains, Northern Bohemia. Qualitative and quantitative data on throughfall for the period November 1989–October 1990 are presented. Weighted averages of SO ₄ ^2? and NO ₃ ^? concentrations in the throughfall were 23.05 mg L^?1 and 13.61 mg L^?1 in a beech and 34.41 mg L^?1 and 11.03 mg L^?1 in a spruce forest respectively. Three variables (the molar ratios of K/Na, N_tot/S and N-NO₃/N-NE₄) were used to compare the spruce throughfall quality to that observed in areas with similar however, less damaged spruce stands. Both K/Na and N-NO₃/N-NH₄ ratios clearly decreased with increasing tree damage, the N_tot/S ratio increased. The results suggest that the throughfall in damaged ecosystems of the Erzegebirge region becomes more like a wet precipitation as the tree canopies get sparser and the trees reduce canopy leaching.     

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.