Enhanced Wet Deposition Estimates using Modeled Precipitation Inputs

Effective assessments of linkages between atmospheric deposition and sensitive aquatic and terrestrial ecosystems require a knowledge of spatial patterns in deposition of greater resolution than currently available using point estimates and two-dimensional surface algorithms. A high resolution wet deposition model was developed for the Eastern U.S.A. by incorporating daily precipitation measurements from National Oceanic and Atmospheric Administration (NOAA) monitoring sites located within the Eastern U.S.A.; topographic variables, including elevation, slope, and aspect that affect the amount and distribution of precipitation across the region; and precipitation chemistry data from National Atmospheric Deposition Program (NADP) sites within and adjacent to the region. Model performance, which was tested against independent measurements from three physiographic regions of the eastern U.S.A., revealed a statistically significant reduction in interpolation error compared to traditional two-dimensional surface algorithms.     

Efficacy of a Biomonitoring (Moss Bag) Technique for Determining Element Deposition Trends on a Mid-Range (375 Km) Scale

National networks detect multi-state trends in element deposition using direct measurement methods. Biomonitoring techniques have been used to examine deposition in local areas and around point sources. We sought to determine the efficacy of a moss bag technique to detect element deposition trends on a mid-range (state) scale, and to compare these results with those of the National Acid Deposition Program/National Trends Network (NADP/NTN, 1999). We sampled heavy metals, sulfur, and nitrogen deposition (21 elements) using mesh bags containing Sphagnum russowii at nine sites, over a 375 km transect crossing southern Wisconsin (upper Midwest, USA). We found statistically significant trends of decreasing deposition in a northwesterly direction for 13 elements: Al, B, Ca, Cd, Co, Cu, Cr, Fe, Mg, Mn, Ni, S, and Zn. Six of these have moderate to large changes in concentration (14–37%). The trends for Ca, Mg, and S are consistent with regional deposition patterns in 1998 isopleth maps from the NADP/NTN (1999) which are derived from a sampling array far less dense than the transect sites. This national network indicates that Ca and Mg increase to the southeast, beyond Wisconsin borders. The fact that the present study demonstrates strong correlations between both of these elements (Ca and Mg) and Al, B, Cr, Cu, Fe, Mn, Ni, and Zn (mean r for all correlations = 0.75, p < 0.02) implies that these correlated elements also increase to the southeast in neighboring states.     

A Comparison of the Precipitation Chemistry Measurements Obtained by the CAPMoN and NADP/NTN Networks

Precipitation chemistry measurementsobtained by the Canadian Air and PrecipitationMonitoring Network (CAPMoN) and the U.S. NationalAtmospheric Deposition Program/National Trends Network(NADP/NTN) have been examined using more than 7 yrof collocated data from two sites, namely, Sutton,Quebec, Canada and State College, Pennsylvania, U.S.A.In the case of the CAPMoN data, weeklyprecipitation-weighted mean concentrations, totalsample depths and total standard gauge depths werecomputed from daily data and compared to thecorresponding weekly sampling data of the NADP/NTNnetwork. Seasonal and annual precipitation-weightedmean concentrations and deposition values were alsocomputed for both networks and compared. Statisticallysignificant between-network biases were found to existin the weekly results for most of the measuredvariables, particularly standard gauge depth, sampledepth, pH, H⁺, NO₃ ^-,NH₄ ⁺,Na⁺; the NADP/NTN values were consistently lowerthan those of CAPMoN with the exception of pH andNa⁺. The magnitude of the biases was less than35% of the median CAPMoN weekly value for the 7 yr. For most of the measured parameters, thevariability of the between-network differencesrepresented less than 20% of the median CAPMoN weeklyvalue. Both the between-network biases andvariabilities were functions of several physicalparameters, the most dominant being the sample depthand the ionic concentration. For seasonal and annualdeposition values, statistically significantbetween-network biases were found for H⁺,SO₄ ^2-, NO₃ ^-,Ca²⁺,NH₄ ⁺ for both periods; for Mg²⁺ andK⁺ for seasonal data; and Cl^- for yearlydata, with the NADP/NTN deposition values being lowerthan those of CAPMoN. The relative biases ranged from7 to 37%. Part of the between-network bias in thedeposition estimates was directly attributable to astrong bias in the standard gauge depths of the two networks.     

A Global Overview of Atmospheric Acid Deposition Fluxes

This paper presents a summary of globalacid deposition flux data taken from a globalassessment report on acid deposition prepared forUNEP/WMO (Whelpdale and Kaiser, 1996). There is a largevariation in the spacial coverage and reliability ofmonitoring around the world. Many more stationsmeasure wet deposition than collect appropriate datafor estimating dry deposition. The widespread regionswith highest precipitation concentrations anddeposition fluxes of sulphate and nitrate coincideclosely with the regions of highest density ofSO₂ and NO_x precursor emissions occurringprimarily in the mid-latitude, northern hemispherebelt where a large fraction of the worlds fossilfuels is consumed. Organic acids in precipitation makea minor contribution to acidity (<20%) inindustrial regions, but in the rest of the world theyare of same order, or even exceed, inorganic acids.Less is known about dry deposition, but it appears topredominate near strong emission sources with wetdeposition predominating farther downwind. The molarratio of the N/S contribution to acidic deposition isclose to 1.0 over large areas of Europe and NorthAmerica, but is highly variable elsewhere, beinghighest in equatorial regions due to biomass burningand lowest near smelters and other large sources of SO₂.     

Estimated Variability of National Atmospheric Deposition Program/Mercury Deposition Network Measurements Using Collocated Samplers

The National Atmospheric Deposition Program/Mercury Deposition Network (MDN) provides long-term, quality-assured records of mercury in wet deposition in the USA and Canada. Interpretation of spatial and temporal trends in the MDN data requires quantification of the variability of the MDN measurements. Variability is quantified for MDN data from collocated samplers at MDN sites in two states, one in Illinois and one in Washington. Median absolute differences in the collocated sampler data for total mercury concentration are approximately 11% of the median mercury concentration for all valid 1999–2004 MDN data. Median absolute differences are between 3.0% and 14% of the median MDN value for collector catch (sample volume) and between 6.0% and 15% of the median MDN value for mercury wet deposition. The overall measurement errors are sufficiently low to resolve between NADP/MDN measurements by ±2 ng·l⁻¹ and ±2 μg·m⁻²·year⁻¹, which are the contour intervals used to display the data on NADP isopleths maps for concentration and deposition, respectively.     

Environmental indicators for long-range atmospheric transported heavy metals based on national moss surveys

Environmental indicators for long-range atmospheric transported heavy metals have been developed. The indicators are based on data for Pb and Cd from national moss surveys which are performed regularly in Norway. The interpolation programme kriging has been used to transform the data from irregular grids to regular grids. Contour maps have been produced, and areas above estimated background levels for Pb and Cd in mosses have been calculated. The indicators are used to characterise the atmospheric deposition of long-range atmospheric transported heavy metals and monitor the changes with time.     

Changes in precipitation chemistry in Lithuania for 1981-2004

This paper considers the spatial and temporal variability in concentrations of the potentially acidifying ions in precipitation in Lithuania during the 1981-2004 period. Chemical analysis of precipitation included measurements of pH, conductivity, sulfate (SO4(2-)), nitrate (NO3-), chloride (Cl-), ammonium (NH4+), sodium (Na+), potassium (K+), and calcium (Ca2+). Temporal trends in the potentially acidifying ion concentrations in precipitation and wet deposition were evaluated using the non-parametric Mann-Kendall test and Sen's slope estimator. A statistically significant decline was observed in non-sea salt sulfate (nssSO4(2-)) and hydrogen (H+) ions concentrations (82% and 79%, respectively) and wet depositions (88% and 74%, respectively). Temporal trends both in concentration and wet deposition of nitrate and ammonium were not as pronounced as trends in sulfate concentration. Analysis of air mass backward trajectories was applied to reveal the influence of air mass originating in different regions on wet deposition of acidifying species in Lithuania. Sector analysis clearly showed that wet deposition of sulfur and nitrogen in Lithuania is to a large extent anthropogenic and the main source regions of acidifying species contributing to wet deposition in Lithuania are in South and Central Europe.     

Comparison of stochastic and deterministic methods for mapping groundwater level spatial variability in sparsely monitored basins

In sparsely monitored basins, accurate mapping of the spatial variability of groundwater level requires the interpolation of scattered data. This paper presents a comparison of deterministic interpolation methods, i.e. inverse distance weight (IDW) and minimum curvature (MC), with stochastic methods, i.e. ordinary kriging (OK), universal kriging (UK) and kriging with Delaunay triangulation (DK). The study area is the Mires Basin of Mesara Valley in Crete (Greece). This sparsely sampled basin has limited groundwater resources which are vital for the island’s economy; spatial variations of the groundwater level are important for developing management and monitoring strategies. We evaluate the performance of the interpolation methods with respect to different statistical measures. The Spartan variogram family is applied for the first time to hydrological data and is shown to be optimal with respect to stochastic interpolation of this dataset. The three stochastic methods (OK, DK and UK) perform overall better than the deterministic counterparts (IDW and MC). DK, which is herein for the first time applied to hydrological data, yields the most accurate cross-validation estimate for the lowest value in the dataset. OK and UK lead to smooth isolevel contours, whilst DK and IDW generate more edges. The stochastic methods deliver estimates of prediction uncertainty which becomes highest near the southeastern border of the basin.     

A Preliminary Assessment of the Montréal Process Indicators of Air Pollution for the United States

Air pollutants pose a risk to forest health and vitality in the United States. Here we present the major findings from a national scale air pollution assessment that is part of the United States' 2003 Report on Sustainable Forests. We examine trends and the percent forest subjected to specific levels of ozone and wet deposition of sulfate, nitrate, and ammonium. Results are reported by Resource Planning Act (RPA) reporting region and integrated by forest type using multivariate clustering. Estimates of sulfate deposition for forested areas had decreasing trends (1994-2000) across RPA regions that were statistically significant for North and South RPA regions. Nitrate deposition rates were relatively constant for the 1994 to 2000 period, but the South RPA region had a statistically decreasing trend. The North and South RPA regions experienced the highest ammonium deposition rates and showed slightly decreasing trends. Ozone concentrations were highest in portions of the Pacific Coast RPA region and relatively high across much of the South RPA region. Both the South and Rocky Mountain RPA regions had an increasing trend in ozone exposure. Ozone-induced foliar injury to sensitive species was recorded in all regions except for the Rocky Mountain region. The multivariate analysis showed that the oak-hickory and loblolly-shortleaf pine forest types were generally exposed to more air pollution than other forest types, and the redwood, western white pine, and larch forest types were generally exposed to less. These findings offer a new approach to national air pollution assessments and are intended to help focus research and planning initiatives related to air pollution and forest health.     

Extent of acidification in Southwestern Québec lakes

This paper presents the results from the first two areas covered by the statistically-oriented Québec Spatial Lake Acidity Monitoring Network (RESSALQ). It is used in combination with the existing LRTAP-Québec temporal network, the Québec precipitation sampling network (REPQ) and a dose-effect model (SIGMA/SLAM) in order to assess the global extent of damages related to acidity, to detect changes in water quality, and to measure the effects of wet sulphate deposition reduction and those of sulphate target loadings on lake acidity. Results obtained with this network were also used in combination with data issued from the Eastern Lake Survey, in order to establish the relative acidity and sensitivity status of lakes in Eastern North America. While Florida has the highest proportion of very acidic and very sensitive lakes, Québec has a higher overall proportion of sensitive and acidic lakes compared to other areas of the United States.     

Deposition and storage of solid-bound heavy metals in the floodplains of the River Geul (the Netherlands)

Because of past mining activities, the floodplains of the River Geul are polluted with heavy metals. The continuous supply of fresh sediments during floods has caused the floodplain soils to exhibit large quality variations in time. By measurements of ¹³⁷Cs deposition rates in part of the floodplain area were determined at 0.4 to 2.7 cm yr^–1. Analysis of soil metal concentrations at various depths at 65 locations, revealed that the upper 40 cm of the soil profile deposited during the past 30–45 yr, exhibit the highest metal levels. The geostatistical interpolation technique kriging was used to map actual and past pollution patterns. It was shown that, as a result of variable deposition rates, the spatial correlation structure of soil metal concentrations becomes less clear with increasing depth/age. Kriged maps of average metal concentrations in the upper 100 cm of the soil profile provided the basis for the calculation of the mass storage of heavy metals.     

Combining mapped and statistical data in forest ecological inventory and monitoring – supplementing an existing system

A forest ecological inventory and monitoring system combining information derived from maps and samples is proposed based on ecosystem regions (Bailey, 1994). The system extends the design of the USDA Forest Service Region 6 Inventory and Monitoring System (R6IMS) in the Pacific Northwest of the United States. The key uses of the information are briefly discussed and expected results are illustrated with examples. The system is flexible, allowing regions based on ecological considerations to be modified. Sampling intensities that are affordable are likely to be insufficient to provide meaningful estimates for key parameters relating to rare and endangered species, watersheds, and other ecological units. Methods are proposed for collecting additional information in follow-up surveys and combining it with relevant information obtained in R6IMS. Near-continuous information on weather and possible pollution variables recorded by instruments at sampling sites is needed to develop meaningful models to understand what is happening in the ecoregions. R6IMS and the proposed additions constitute a dynamic system which will be modified further as data are analyzed.     

Sulphate, Nitrogen and Base Cation Budgets at 21 Forested Catchments in Canada, the United States and Europe

To assess the concern over declining base cation levels in forest soils caused by acid deposition, input-output budgets (1990s average) for sulphate (SO₄), inorganic nitrogen (NO₃-N; NH₄-N), calcium (Ca), magnesium (Mg) and potassium (K) were synthesised for 21 forested catchments from 17 regions in Canada, the United States and Europe. Trend analysis was conducted on monthly ion concentrations in deposition and runoff when more than 9 years of data were available (14 regions, 17 sites). Annual average SO₄ deposition during the 1990s ranged between 7.3 and 28.4 kg ha⁻¹ per year, and inorganic nitrogen (N) deposition was between 2.8 and 13.8 kg ha⁻¹ per year, of which 41–67% was nitrate (NO₃-N). Over the period of record, SO₄ concentration in deposition decreased in 13/14 (13 out of 14 total) regions and SO₄ in runoff decreased at 14/17 catchments. In contrast, NO₃-N concentrations in deposition decreased in only 1/14 regions, while NH₄-N concentration patterns varied; increasing at 3/14 regions and decreasing at 2/14 regions. Nitrate concentrations in runoff decreased at 4/17 catchments and increased at only 1 site, whereas runoff levels of NH₄-N increased at 5/17 catchments. Decreasing trends in deposition were also recorded for Ca, Mg, and K at many of the catchments and on an equivalent basis, accounted for up to 131% (median 22%) of the decrease in acid anion deposition. Base cation concentrations in streams generally declined over time, with significant decreases in Ca, Mg and K occurring at 8, 9 and 7 of 17 sites respectively, which accounted for up to 133% (median 48%) of the decrease in acid anion concentration. Sulphate export exceeded input at 18/21 catchments, likely due to dry deposition and/or internal sources. The majority of N in deposition (31–100%; median 94%) was retained in the catchments, although there was a tendency for greater NO₃-N leaching at sites receiving higher (<7 kg ha^-1 per year) bulk inorganic N deposition. Mass balance calculations show that export of Ca and Mg in runoff exceeds input at all 21 catchments, but K export only exceeds input at 16/21 sites. Estimates of base cation weathering were available for 18 sites. When included in the mass balance calculation, Ca, Mg and K exports exceeded inputs at 14, 10 and 2 sites respectively. Annual Ca and Mg losses represent appreciable proportions of the current exchangeable soil Ca and Mg pools, although losses at some of the sites likely occur from weathering reactions beneath the rooting zone and there is considerable uncertainty associated with mineral weathering estimates. Critical loads for sulphur (S) and N, using a critical base cation to aluminium ratio of 10 in soil solution, are currently exceeded at 7 of the 18 sites with base cation weathering estimates. Despite reductions in SO₄ and H⁺ deposition, mass balance estimates indicate that acid deposition continues to acidify soils in many regions with losses of Ca and Mg of primary concern. The U.S. Government's right to retain a non-exclusive, royalty free licence in and to any copyright is acknowledged. The Canadian Crown reserves the right to retain a non-exclusive, royalty free licence in and to any copyright.     

Estimating Trophic State Proportions of a Regional Lake Population: Are Larger Samples Always Better?

During the summers of 1991–1994, the Environmental Monitoringand Assessment Program (EMAP) sampled 344 lakes throughout thenortheastern United States using a proportional stratified sampling design based on lake size. Approximately one-quarter ofthe 344 lakes were sampled each year (4 years) for totalphosphorus to determine the proportion (and associated95% confidence intervals) of the northeast lake population 1ha (11,076 ± 1,699 lakes) that was in oligotrophic,mesotrophic, eutrophic, or heupereutropic (4 classes) conditionaccording to the total phosphorus criteria of the North AmericaLake Manegement Society. Estimates for the second, third, andfourth yr were developed as cumulative of the previous yrsamples and the current yr samples for the northeast as a wholeand for each of its three ecoregions (4 regions). New confidence intervals were computed for each cumulative yrcondition estimate. This produced a total (4 years × 4classes × 4 regions) of 64 cumulative yr tropic conditionestimates. Confidence intervals for 21% of these estimates didnot shorten with increased sample size. This phenomena raisedquestions about the accuracy of estimates based on cumulativesampling procedures. We explain why and how the phenomenon comesabout with both straight random and proportional randomsampling. Further, we present an example of the effects thisphenomenon has on lake tropic state condition estimates in thenortheastern United States.     

Assessment of the redistribution of soil carbon using a new index—a case study in the Haihe River Basin,North China

Soil carbon redistribution is an important process in the terrestrial carbon cycle. This study describes a new index, soil carbon redistribution (SCR) index, that can be used to assess long-term soil carbon redistribution at a large watershed scale. The new index is based on the theoretical preconditions that soil carbon redistribution is mainly controlled by vegetation type, precipitation, topography/slope, and soil carbon concentration. The Haihe River Basin served as an example for this analysis. The SCR index was calculated, and a GIS-based map shows its spatial patterns. The results suggested that soil carbon was usually prone to being carried away from mountainous regions with natural vegetation, while it was prone to deposition in the plain and plateau regions with cultivated vegetation. The methods in the paper offer a tool that can be used to quantify the potential risk where soil carbon is prone to being carried away and deposited in a large watershed.     

Comparison of precipitation chemistry measurements obtained by the Canadian Air and Precipitation Monitoring Network and National Atmospheric Deposition Program for the period 1995–2004

Precipitation chemistry and depth measurements obtained by the Canadian Air and Precipitation Monitoring Network (CAPMoN) and the US National Atmospheric Deposition Program/National Trends Network (NADP/NTN) were compared for the 10-year period 1995–2004. Colocated sets of CAPMoN and NADP instrumentation, consisting of precipitation collectors and rain gages, were operated simultaneously per standard protocols for each network at Sutton, Ontario and Frelighsburg, Ontario, Canada and at State College, PA, USA. CAPMoN samples were collected daily, and NADP samples were collected weekly, and samples were analyzed exclusively by each network’s laboratory for pH, H^?+?, Ca^2?+?, Mg^2?+?, Na^?+?, K^?+?, $\text{NH}_{4}^{+}$ , Cl^???, $\text{NO}_{3}^{-}$ , and $\text{SO}_{4}^{2-}$ . Weekly and annual precipitation-weighted mean concentrations for each network were compared. This study is a follow-up to an earlier internetwork comparison for the period 1986–1993, published by Alain Sirois, Robert Vet, and Dennis Lamb in 2000. Median weekly internetwork differences for 1995–2004 data were the same to slightly lower than for data for the previous study period (1986–1993) for all analytes except $\text{NO}_{3}^{-}$ , $\text{SO}_{4}^{2-}$ , and sample depth. A 1994 NADP sampling protocol change and a 1998 change in the types of filters used to process NADP samples reversed the previously identified negative bias in NADP data for hydrogen-ion and sodium concentrations. Statistically significant biases (α = 0.10) for sodium and hydrogen-ion concentrations observed in the 1986–1993 data were not significant for 1995–2004. Weekly CAPMoN measurements generally are higher than weekly NADP measurements due to differences in sample filtration and field instrumentation, not sample evaporation, contamination, or analytical laboratory differences.     

Spatial analysis and mapping the annual mean concentrations of acidity and major ions in precipitation over the United Kingdom in 1986

The composition of precipitation is being monitored in collectors sited throughout the United Kingdom. In the first year, 1986, hydrogen ion, nitrate, ammonium and non-marine sulphate were measured in samples from 47 sites and annual mean concentrations determined. Spatial analysis based on Regionalized Variable Theory revealed autocorrelation in all four ions and reasonable bounded models were fitted to the sample variogram of all four. These were then used to estimate values of a fine mesh grid by simple kriging, and the estimates were then contoured. The estimation errors were similarly mapped, and both sets of maps are presented. The maps show that concentrations of these ions are greatest in eastern parts of the country, as expected from consideration of European emissions and weather patterns. For the first time estimation errors were also mapped and show how the network could be improved.     

The temporal changes in road stormwater runoff quality and the implications to first flush control in Chongqing, China

This study investigates the quality of stormwater runoff from a driveway in the southwest mountainous urban area of Chongqing, China, from 2010 to 2011. The results showed that the mean concentrations of chemical oxygen demand (COD), total nitrogen (TN), and total phosphorus (TP) were 4.1, 2.4, and 2.2 times the grade V levels of the national surface water standard of China. The pollutant concentration peak preceded or synchronized with the rainfall intensity peak and occurred 10 min after the runoff started. The significant high pollutant concentration in the initial stage of the rainfall suggested that first flush control is necessary, especially for the most polluted constitutes, such as total suspended solids, COD, and TN. Three potential pollution sources were identified: the atmospheric dry and wet deposition (TN, NO₃ ^?-N, NH₄ ⁺-N, and DCu), the road sediment and materials (total suspended solids, COD, and TP), and the vehicle emissions (DPb and DZn). Therefore, this study indicates that reductions in road sediments and material pollution and dry and wet deposition should be the priority factors for pollution control of road stormwater runoff in mountainous urban areas.     

Monitoring global change: Comparison of forest cover estimates using remote sensing and inventory approaches

Satellite-based remote sensing offers great potential for frequent assessment of forest cover over broad spatial scales, however, calibration and validation using ground-based surveys are needed. In this study, forest cover estimates for the United States from a recently developed land surface cover map generated from satellite remote sensing data were compared to state-level inventory data from the U.S. National Resources Planning Act Timber Database. The land cover map was produced at the U.S. Geological Survey EROS Data Center and is based on imagery from the AVHRR sensor (spatial resolution 1.1 km). Vegetation type was classified using the temporal signal in the Normalized Difference Vegetation Index derived from AVHRR data. Comparisons revealed close agreement in the estimate of forest cover for extensively forested states with large polygons of relatively similar vegetation such as Oregon. Larger forest cover differences were observed in other states with some regional patterns in the level of agreement apparent.Comparisons in inventory- and remote sensing-based estimates of current forested area with potential vegetation maps indicated the magnitude of past land use change and the potential for future changes. The remote sensing approach appears to hold promise for conducting surveys of forest cover where inventory data are limited or where rates of vegetation change, due to human or climatic factors, are rapid.     

Contemporary estimates of atmospheric nitrogen deposition to the watersheds of New York State, USA

Atmospheric inputs of reactive nitrogen (N) to ecosystems are a particular concern in the northeastern USA, including New York State, where rates of atmospheric N deposition are among the highest in the nation. We calculate the seasonal and annual spatial variations of contemporary inorganic atmospheric N deposition loading to multi-scale watersheds across New York State using numerous monitoring datasets of precipitation and ambient atmospheric N concentrations. Our models build upon and refine previous efforts estimating the spatial distribution of N deposition. Estimates of total inorganic wet deposition (NH4-N + NO3-N) across New York ranged from 4.7 to 10.5 kg ha(-1) yr(-1) under contemporary conditions (averaged 2002-2004), and both seasonal and annual predicted rates of inorganic N deposition (NH4-N, NO3-N, and total) fit relatively well with that of observed measurements. Our results suggest that "hot spots" of N deposition are, for the most part, spatially distributed according to geographic positions (i.e., relative location from sources and the Great Lakes system) and elevation. We also detect seasonal variations in deposition, showing that total wet atmospheric inorganic N deposition inputs to watersheds (extracted from the four-digit HUC calculations) are highest during the spring (mean = 2.4 kg ha(-1), stddev = 0.29) and lowest during the winter months (mean = 1.4 kg ha(-1), stddev = 0.23). Results also suggest that wet NO3(-) consistently comprises a slightly higher proportion of wet N deposition than wet NH4+ throughout watersheds of New York, ranging from 2.5 to 6.1 kg NO3-N ha(-1) yr(-1) compared to NH4+, which ranges from 2.2 to 4.4 kg NH4-N ha(-1) yr(-1).