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.     

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 ^? .     

Adverse Effects of Ammonia on Nitrification Process: the Case of Chinese Shallow Freshwater Lakes

Nitrification is a process in which ammonia is oxidized to nitrite (NO ₂ ^? ) that is further oxidized to nitrate (NO ₃ ^? ). The relations between these two steps and ambient ammonia concentrations were studied in surface water of Chinese shallow lakes with different trophic status. For the oxidations of both ammonia and NO ₂ ^? , more eutrophic lakes generally showed significantly higher potential and actual rates, which was linked with excessive ammonia concentrations. Additionally, both potential and actual rates for ammonia oxidation were higher than those for NO ₂ ^? oxidation in the more eutrophic lakes, while in the lakes with lower trophic status, both potential and actual rates for ammonia oxidation were almost equivalent to those for NO ₂ ^? oxidation. This can be explained by the excessive unionized ammonia (NH₃) concentration that inhibits nitrite-oxidizing bacteria in the more eutrophic lakes. The laboratory experiment with different ammonia concentrations, using the surface water in a eutrophic lake, showed that ammonia oxidation rates were proportional to the ammonia concentrations, but NO ₂ ^? oxidation rates did not increase in parallel. Furthermore, NO ₂ ^? oxidation was less associated with particles in natural water of the studied lakes. Without effective protection, it would be selectively inhibited by the excessive ammonia in hypereutrophic lakes, resulting in NO ₂ ^? accumulation. Shortly, the increased concentrations of ammonia cause a misbalance between the NO ₂ ^? -producing and the NO ₂ ^? -consuming processes, thereby exacerbating the lake eutrophication.     

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.     

Monitoring and Modeling Nitrate Persistence in a Shallow Aquifer

A modeling study on fertilizer by-products fate and transport was performed in an unconfined shallow aquifer equipped with a grid of 13 piezometers. The field site was located in a former agricultural field overlying a river paleochannel near Ferrara (Northern Italy), cultivated with cereals rotation until 2004 and then converted to park. Piezometers were installed in June 2007 and were monitored until June 2009 via pressure transducer data loggers to evaluate the temporal and spatial variation of groundwater heads, while an onsite meteorological station provided data for recharge rate calculations via unsaturated zone modeling. The groundwater composition in June 2007 exhibited elevated nitrate (NO ₃ ^? ) and chloride (Cl^?) concentrations due to fertilizer leaching from the top soil. The spatial distribution of NO ₃ ^? and Cl^? was heterogeneous and the concentration decreased during the monitoring period, with NO ₃ ^? attenuation (below 10?mg/l) after 650?days. A transient groundwater flow and contaminant transport model was calibrated versus observed heads and NO ₃ ^? and Cl^? concentrations. Cl^? was used as environmental tracer to quantify groundwater flow velocity and it was simulated as a conservative species. NO ₃ ^? was treated as a reactive species and denitrification was simulated with a first order degradation rate constant. Model calibration gave a low denitrification rate (2.5e^?3 mg-NO ₃ ^? /l/d) likely because of prevailing oxic conditions and low concentration of dissolved organic carbon. Scenario modeling was implemented with steady state and variable flow time discretization to identify the mechanism of NO ₃ ^? attenuation. It was shown that transient piezometric conditions did not exert a strong control on NO ₃ ^? clean up time, while transient recharge rate did, because it is the main source of unpolluted water in the domain.     

Effect of an attendant anion on the balance of cations in the soil-solution system with an ordinary chernozem as an example

The effect of different anions on the balance of heavy metal cations in the soil-solution system has been assessed under model laboratory conditions. It has been found that the uptake of the Cu, Zn, and Pb cations by an ordinary chernozem from solutions of different salts is accompanied by the displacement of the exchangeable cations to the solution in the following order: Ca²⁺ > Mg²⁺ > Na⁺ > K⁺. The sum of the displaced exchangeable cations in most cases exceeds the amount of the adsorbed heavy metal cations. According to the effect of the anions on the displacing capacity of the metal cations, the following series are formed: for copper, SO ₄ ^2? ? Cl^? > OAc^? > NO ₃ ^? ; for lead, Cl^? ? NO ₃ ^? > OAc^?; and, for zinc, SO ₄ ^2? ? Cl^? ? OAc^? > NO ₃ ^? .     

Interaction between nitrogen fertilization,rainfall and groundwater pollution in sandy soil

A 2 yr field study on the influence of N fertilization and rainfall on groundwater pollution was carried out in the sandy area of Belgium. The NO _inf3 ^sup? -N and Cl^? content of the groundwater at 0.5, 1.0, 1.5, and 2.0 m depths was monitored every two weeks on a field, grown with barley in 1980 and with maize in 1981. Turnips for cattle feed were grown in between the two crops. The total annual rainfall during the period under study was about 800 mm. The NO _inf3 ^sup? -N content at all depths was at all times above 11.3 mg NO _inf3 ^sup? -N dm^?3, the WHO safe limit. Fluctuation of the NO _inf3 ^sup? -N content occurred mainly at 0.5 and 1.0 m. The concentration at 1.5 and 2.0 m depths was higher most of the time than at 0.5 and 1.0 m. Leaching of NO _inf3 ^sup? -N into deeper layers occurred when there was heavy rainfall. There was no important loss of NO _inf3 ^sup? -N through denitrification at 1.5 and 2.0 m depths.     

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.     

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.     

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.     

Fluid Catalytic Cracking Unit Emissions and Their Impact

A constructed wetland composed of a pond- and a marsh-type wetland was employed to remove nitrogen (N) and phosphorus (P) from effluent of a secondary wastewater treatment plant in Korea. Nutrient concentrations in inflow water and outflow water were monitored around 50 times over a 1-year period. To simulate N and P dynamics in a pond- and a marsh-type wetland, mesocosm experiments were conducted. In the field monitoring, ammonium (NH ₄ ⁺ ) decreased from 4.6 to 1.7 mg L^?1, nitrate (NO ₃ ^? ) decreased from 6.8 to 5.3 mg L^?1, total N (TN) decreased from 14.6 to 10.1 mg L^?1, and total P (TP) decreased from 1.6 to 1.1 mg L^?1. Average removal efficiencies (loading basis) for NO ₃ ^? , NH ₄ ⁺ , TN, and TP were over 70%. Of the environmental variables we considered, water temperature exhibited significant positive correlations with removal rates for the nutrients except for NH ₄ ⁺ . Results from mesocosm experiments indicated that NH ₄ ⁺ was removed similarly in both pond- and marsh-type mesocosms within 1 day, but that NO ₃ ^? was removed more efficiently in marsh-type mesocosms, which required a longer retention time (2?C4 days). Phosphorus was significantly removed similarly in both pond- and marsh-type mesocosms within 1 day. Based on the results, we infer that wetland system composed of a pond- and a marsh-type wetland consecutively can enhance nutrient removal efficiency compared with mono-type wetland. The reason is that removal of NH ₄ ⁺ and P can be maximized in the pond while NO ₃ ^? requiring longer retention time can be removed through both pond and marsh. Overall results of this study suggest that a constructed wetland composed of a pond- and a marsh-type wetland is highly effective for the removal of N and P from effluents of a secondary wastewater treatment plant.     

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? .     

Effects of nitrogen dioxide on selected soil processes

Nitrogen dioxide gas was rapidly absorbed by soil. After a 15 min incubation at 25°C, soil at a moisture content of 16% absorbed 99% of the NO₂ introduced into the gas-phase volume of a closed system. The presence of microorganisms hatl no influence on the rate of absorption of the gas by soil. The absorption of NO₂ by sandy clay loam soil was not an oxygen- or temperature-dependent process nor did it depend upon the moisture content of the soil. These physical factors acquired significance only in determining the initial rate of absorption of the gas and the rate at which NO₂ diffused through the soil. Exposure of soil to NO₂ resulted in substantial increases in the levels of NO _inf2 ^sup? N in the soil. Chemical oxidation of the NO _inf2 ^sup? N resulted in an increase in NO _inf3 ^sup? N levels. During a 14-day incubation, NO _inf2 ^sup? N concentrations in sterile soil exposed to an atmosphere containing 100 μg ml^?1 of NO₂ decreased from 190 μg g^?1 of soil to 105 μg g^?1 with an accompanying increase in NO _inf3 ^sup? N from 2 μg g^? ₁ to 63 μg g^?1 of soil. Nitrogen dioxide severely inhibited the growth of both aerobic and anaerobic asymbiotic N₂-fixing bacteria in soil. After a 48 h incubation at 25°C, soil aggregates exposed to an atmosphere containing 100 μg ml^?1 of NO₂ contained 88% and 98% fewer aerobic and anaerobic N₂-fixing bacteria, respectively. C₂H₂-reduction measurements showed that nitrogenase synthesis and activity in artificial soil aggregates amended with 2% glucose were inhibited by 20% and 48%, respectively, when exposed to atmospheric concentrations of 35 and 3.5 μg ml^?1 of NO₂, respectively.     

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.     

Analysis of Decadal Time Series in Wet N Concentrations at Five Rural Sites in NE Spain

Nitrogen emissions have grown in Spain during the last 15 years. As precipitation scavenges gases and aerosols from the atmosphere, an effect on rainwater concentrations can be expected. However, time-series studies on wet N concentrations in the Iberian Peninsula are very scarce. This paper aims to fill this gap by analysing weekly rainfall N concentrations at a set of rural sites in Catalonia (NE Spain) from 1995/1996 to 2007 and a forest site monitored from 1983 to 2007. The sites encompass a range of rural environments and climate conditions, from the inland pre-Pyrenees (Sort) to the Mediterranean coast (Begur) and from north (Sort and Begur) to central (Palautordera and La Castanya) and south Catalonia (La Senia). We found a 1-year cycle for concentrations of NH ₄ ⁺ and NO ₃ ^? whereby higher values were reached at the end of spring–early summer, except at the easternmost coastal site of Begur. Weekly NH ₄ ⁺ concentrations decreased with time at all sites (except at La Senia) whilst NO ₃ ^? concentrations increased at all sites during the same period. Rainfall SO ₄ ^2? concentrations decreased with time at all sites. The opposite trends in NO ₃ ^? and SO ₄ ^2? concentrations determined a shift in the relative acid contribution of those anions during the 12–13-year period. To interpret the increasing trend, mean annual NO ₃ ^? concentrations were regressed against NO₂ Spanish emissions and to some indicators of local anthropogenic activity. The increase at Sort and Palautordera showed good correlation with local anthropogenic indicators. Wet inorganic N deposition ranged between 4.2 and 6.7 kg ha^?1 year^?1. When including estimates of dry deposition, total annual deposition rose up to 10–20 kg ha^?1 year^?1, values that have been found to initiate adverse effects on Mediterranean-type forest ecosystems.     

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.     

Foliar Nitrogen Uptake from Wet Deposition and the Relation with Leaf Wettability and Water Storage Capacity

This study assessed the foliar uptake of ¹⁵N-labelled nitrogen (N) originating from wet deposition along with leaf surface conditions, measured by wettability and water storage capacity. Foliar ¹⁵N uptake was measured on saplings of silver birch, European beech, pedunculate oak and Scots pine and the effect of nitrogen form (NH ₄ ⁺ or NO ₃ ^? ), NH ₄ ⁺ to NO ₃ ^? ratio and leaf phenology on this N uptake was assessed. Next to this, leaf wettability and water storage capacity were determined for each tree species and phenological stage, and the relationship with ¹⁵NH ₄ ⁺ and ¹⁵NO ₃ ^? uptake was examined. Uptake rates were on average five times higher (p?<?0.05) for NH ₄ ⁺ than for NO ₃ ^? and four times higher for deciduous species than for Scots pine. Developing leaves showed lower uptake than fully developed and senescent leaves, but this effect was tree species dependent. The applied NH ₄ ⁺ to NO ₃ ^? ratio did only affect the amount of N uptake by senescent leaves. The negative correlation between measured leaf contact angles and foliar N uptake demonstrates that the observed effects of tree species and phenological stage are related to differences in leaf wettability and not to water storage capacity.     

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.     

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).