Aerodynamic Gradient Method Research Articles

Increasing complexity in Aerodynamic Gradient flux calculations inside the roughness sublayer applied on a two-year dataset

Over tall canopies such as forests the atmospheric surface layer is subdivided into an inertial sublayer (ISL) and a roughness sublayer (RSL). Inside the RSL the classic aerodynamic gradient method using Monin-Obukhov similarity theory (MOST) by itself does not represent the gradient well and is insufficient to calculate fluxes. Over the past decades multiple studies have proposed methods to extend MOST to account for the different turbulent conditions within the RSL, containing a wide range of approaches and complexity. In this study we investigate how much complexity is necessary to calculate the flux more accurately and what we can learn from the respective complexity. A large dataset is required to assess the statistical robustness of the respective complexity during different environmental conditions. To this end, we study and apply the effect of forest roughness and directional heterogeneity in our flux calculations on a two-year dataset (2009-2010) of the sensible heat flux measured over a Douglas fir forest in the Netherlands. We apply standard MOST, an observational based method (the α-factor) and a physically based method (Harman and Finnigan, 2007, 2008) (hereafter HF07/08) together with a range of methods for the displacement height (d). Our results show that both a simple method (the α-factor) and a complex method (HF07/08) are able to more accurately represent the flux but that, as expected, standard MOST (regardless of the method estimating d) alone is insufficient. Both the α-factor and (HF07/08) allow to analyze large scale patterns in canopy turbulence. Differences between the methods lie in the level of detail and practical usability.

Vertical profile and flux measurements of ammonia in a deciduous forest in Japan towards improvement of bi-directional exchange model

Ammonia (NH3) is a major component of reduced nitrogen. A bi-directional exchange of NH3 takes place between the atmosphere and surface. Although the study of reduced nitrogen is gaining prominence in recent years, quantification of NH3 deposition is technically challenging due to its complex properties; consequently, this generates significant uncertainty regarding the estimation of total nitrogen deposition. Based on past studies, it has been reported that Asia has numerous high-risk nitrogen deposition sites; however, only a few studies have investigated the NH3 exchange in this region. To clarify the exchange process and achieve improved accuracy regarding the estimation of nitrogen deposition in Asia, we conducted measurements of vertical profile and flux of NH3 in a forest in Japan during summer (July 21–August 1, 2015), winter (February 23–February 29, 2016), and autumn (September 27–October 11, 2016). We measured daytime and nighttime NH3 concentrations at four or five heights of an observation tower in the forest by using filter-pack holders, and determined NH3 fluxes by using the aerodynamic gradient method. During daytime, NH3 showed emission above the canopy in summer, and near the forest floor in winter. There was no clear emission trend in autumn. During nighttime, NH3 showed deposition from the top of the canopy to the forest floor for all observed periods. NH3 exchange in the forest possibly had seasonal and diurnal variations. The flux measurements showed large NH3 emissions at daytime in summer and small depositions at nighttime in summer and autumn. Mean flux during the observation periods was 0.026 μg m−2 s−1. The daytime flux during leafy periods was found to have a strong correlation with solar radiation. At daytime in summer, flux also had strong correlations with relative humidity and horizontal wind speed. We also estimated NH3 fluxes in summer by employing a bi-directional exchange model to verify the applicability of the model at the study site. Inferred fluxes obtained via the model showed large emissions during daytime and agreed with the observation results; however, the model could not reproduce the nighttime deposition. This discrepancy was improved by applying more suitable cuticular resistances.

Measurement of HONO flux using the aerodynamic gradient method over an agricultural field in the Huaihe River Basin, China

To investigate nitrous acid (HONO) levels and potential HONO sources above crop rotation fields. The HONO fluxes were measured by the aerodynamic gradient (AG) method from 14 December 2019 to 2 January 2020 over an agricultural field in the Huaihe River Basin. The ambient HONO levels were measured at two different heights (0.15 and 1.5 m), showing a typical diurnal cycle with low daytime levels and high nighttime levels. The upward HONO fluxes were mostly observed during the day, whereas deposition dominated at night. The diurnal variation of HONO flux followed solar radiation, with a noontime maximum of 0.2 nmol/(m2∙sec). The average upward HONO flux of 0.06 ± 0.17 nmol/(m2∙sec) indicated that the agricultural field was a net source for atmospheric HONO. The higher HONO/NO2 ratio and NO2–to–HONO conversion rate close to the surface suggested that nocturnal HONO was formed and released near the ground. The unknown HONO source was derived from the daytime HONO budget analysis, with an average strength of 0.31 ppbV/hr at noontime. The surface HONO flux, which was highly correlated with the photolysis frequency J(NO2) (R2 = 0.925) and the product of J(NO2) × NO2 (R2 = 0.840), accounted for ∼23% of unknown daytime HONO source. The significant correlation between HONO fluxes and J(NO2) suggests a light-driven HONO formation mechanism responsible for the surface HONO flux during daytime.

Forest–atmosphere exchange of reactive nitrogen in a remote region – Part I: Measuring temporal dynamics

Abstract. Long-term dry deposition flux measurements of reactive nitrogen based on the eddy covariance or the aerodynamic gradient method are scarce. Due to the large diversity of reactive nitrogen compounds and high technical requirements for the measuring devices, simultaneous measurements of individual reactive nitrogen compounds are not affordable. Hence, we examined the exchange patterns of total reactive nitrogen (ΣNr) and determined annual dry deposition budgets based on measured data at a mixed forest exposed to low air pollution levels located in the Bavarian Forest National Park (NPBW), Germany. Flux measurements of ΣNr were carried out with the Total Reactive Atmospheric Nitrogen Converter (TRANC) coupled to a chemiluminescence detector (CLD) for 2.5 years. The average ΣNr concentration was 3.1 µg N m−3. Denuder measurements with DELTA samplers and chemiluminescence measurements of nitrogen oxides (NOx) have shown that NOx has the highest contribution to ΣNr (∼51.4 %), followed by ammonia (NH3) (∼20.0 %), ammonium (NH4+) (∼15.3 %), nitrate NO3- (∼7.0 %), and nitric acid (HNO3) (∼6.3 %). Only slight seasonal changes were found in the ΣNr concentration level, whereas a seasonal pattern was observed for the contribution of NH3 and NOx. NH3 showed highest contributions to ΣNr in spring and summer, NOx in autumn and winter. We observed deposition fluxes at the measurement site with median fluxes ranging from −15 to −5 ngNm-2s-1 (negative fluxes indicate deposition). Median deposition velocities ranged from 0.2 to 0.5 cm s−1. In general, highest deposition velocities were recorded during high solar radiation, in particular from May to September. Our results suggest that seasonal changes in composition of ΣNr, global radiation (Rg), and other drivers correlated with Rg were most likely influencing the deposition velocity (vd). We found that from May to September higher temperatures, lower relative humidity, and dry leaf surfaces increase vd of ΣNr. At the measurement site, ΣNr concentration did not emerge as a driver for the ΣNrvd. No significant influence of temperature, humidity, friction velocity, or wind speed on ΣNr fluxes when using the mean-diurnal-variation (MDV) approach for filling gaps of up to 5 days was found. Remaining gaps were replaced by a monthly average of the specific half-hourly value. From June 2016 to May 2017 and June 2017 to May 2018, we estimated dry deposition sums of 3.8 and 4.0 kgNha-1a-1, respectively. Adding results from the wet deposition measurements, we determined 12.2 and 10.9 kgNha-1a-1 as total nitrogen deposition in the 2 years of observation. This work encompasses (one of) the first long-term flux measurements of ΣNr using novel measurements techniques for estimating annual nitrogen dry deposition to a remote forest ecosystem.

Fluxes of H2S and SO2 above a subtropical forest under natural and disturbed conditions induced by temporal land-use change

Hydrogen sulfide (H2S) is one of predominant biogenic sulfur gases, influencing aerosol formation and climate change. There is considerable uncertainty of the global budget of H2S due to limited field data, especially in subtropical forests. In addition, an interaction between soil-emitted H2S and ambient sulfur dioxide (SO2) might exist within forest ecosystems. In this study, the aerodynamic gradient method was applied to consecutively measure H2S and SO2 fluxes above a subtropical forest canopy in Southwest China under natural and disturbed conditions induced by temporal land-use changes. The average H2S concentration and flux under natural conditions were 0.79 ± 0.07 ppbv and 0.04 ± 0.01 g S m−2 yr−1, respectively. The emission was larger than that in most croplands and freshwater wetlands. Vegetation emissions might account for about 26% of the total forest H2S emissions at this site. The deposition of SO2 was likely balanced by H2S oxidization under the forest canopy, with the mean concentration and net flux as 1.23 ± 0.11 ppbv and −0.03 ± 0.10 g S m−2 yr−1, respectively. Under disturbed conditions with soils excavation and scattering on the forest floor, simultaneously high emissions of H2S and SO2 were observed above the canopy, reaching 5.78 ± 0.16 and 1.60 ± 0.87 g S m−2 yr−1, respectively. This suggested that land-use change in subtropical forests might lead to release of legacy S in subsoils to the atmosphere in the form of H2S and SO2. Regarding the widely documented large S accumulation and expanding deforestation across subtropical forests, potentially high emissions of H2S and SO2 from subtropical forests should be carefully considered in regional air quality control and forest management.

Calculation of NH3 Emissions, Evaluation of Backward Lagrangian Stochastic Dispersion Model and Aerodynamic Gradient Method

Two campaigns measuring ammonia (NH3) emissions with different measurement techniques were performed on a large grass field (26 ha) after the application of liquid animal manure. The aim was to compare emissions from a confined area estimated from either (i) concentration measurements, both point and line-integrated measurements, combined with backward Lagrangian stochastic (bLS) dispersion modeling or by (ii) estimation of the vertical flux by the aerodynamic gradient method (AGM) with and without footprint correction approximated by the bLS model estimates of the flux footprint. The objective of the comparison is to establish the best practice to derive NH3 emissions from a large field. NH3 emissions derived from bLS agreed well when comparing point and line-integrated measurements. Simple point measurements combined with bLS yield good emission estimations for the confined area. Without footprint correction, the AGM underestimates the emissions by up to 9% compared to the footprint-corrected AGM results. The sensitivity of the measurement methods makes it possible to quantify NH3 emissions with diurnal patterns even five days after a field application of liquid animal manure under wet conditions. The bLS model proves to be a strong tool to determine the NH3 emissions from point concentration measurements inside a large field after a slurry application.

Concentrations and biosphere–atmosphere fluxes of inorganic trace gases and associated ionic aerosol counterparts over the Amazon rainforest

Abstract. The Amazon rainforest presents a unique, natural laboratory for the study of surface–atmosphere interactions. Its alternation between a near-pristine marine-influenced atmosphere during the wet season and a vulnerable system affected by periodic intrusions of anthropogenic pollution during the dry season provides an opportunity to investigate some fundamental aspects of boundary-layer chemical processes. This study presents the first simultaneous hourly measurements of concentrations, fluxes, and deposition velocities of the inorganic trace gases NH3, HCl, HONO, HNO3, and SO2 as well as their water-soluble aerosol counterparts NH4+, Cl−, NO2-, NO3- and SO42- over the Amazon. Species concentrations were measured in the dry season (from 6 October to 5 November 2017), at the Amazon Tall Tower Observatory (ATTO) in Brazil, using a two-point gradient wet-chemistry instrument (GRadient of AErosols and Gases Online Registration, GRAEGOR) sampling at 42 and 60 m. Fluxes and deposition velocities were derived from the concentration gradients using a modified form of the aerodynamic gradient method corrected for measurement within the roughness sub-layer. Findings from this campaign include observations of elevated concentrations of NH3 and SO2 partially driven by long-range transport (LRT) episodes of pollution and the substantial influence of coarse Cl− and NO3- particulate on overall aerosol mass burdens. From the flux measurements, the dry season budget of total reactive nitrogen dry deposition at the ATTO site was estimated as −2.9 kg N ha-1a-1. HNO3 and HCl were deposited continuously at a rate close to the aerodynamic limit. SO2 was deposited with an average daytime surface resistance (Rc) of 28 s m−1, whilst aerosol components showed average surface deposition velocities of 2.8 and 2.7 mm s−1 for SO42- and NH4+, respectively. Deposition rates of NO3- and Cl− were higher at 7.1 and 7.8 mm s−1, respectively, reflecting their larger average size. The exchange of NH3 and HONO was bidirectional, with NH3 showing emission episodes in the afternoon and HONO in the early morning hours. This work provides a unique dataset to test and improve dry deposition schemes for these compounds for tropical rainforest, which have typically been developed by interpolation from conditions in temperate environments. A future campaign should focus on making similar measurements in the wet season in order to provide a complete view of the annual pattern of inorganic trace gas and coarse aerosol biosphere–atmosphere exchange over tropical rainforest.

The Aerodynamic Gradient Method: Implications of Non-Simultaneous Measurements at Alternating Heights

Flux measurements with the aerodynamic gradient method (AGM) performed with a single analyzer measuring non-simultaneously at two heights have routinely been conducted. This study investigates the effect of this practice with calculations of single analyzer derived fluxes compared to fluxes derived from simultaneous concentration measurements at two heights for NH3. The results show a mean relative difference of less than 7% for the half-hour averaging intervals, whereas the relative difference in the cumulative loss of total ammoniacal nitrogen (TAN) is less than 4%. Scatter plots and linear regression show linear behavior with slope and intercept close to one and zero, respectively. The regression coefficients were between 0.913 and 0.966 for the simulations, but with large deviations for the single half-hour measurement interval. Changes in the starting height and averaging duration at each height for the single analyzer calculations yield small differences, but the effect is minimal compared to the general uncertainty of flux determination with AGM.

Comparison of Ozone Fluxes over a Maize Field Measured with Gradient Methods and the Eddy Covariance Technique

Ozone (O3) fluxes were measured over a maize field using the eddy covariance (EC) technique and gradient methods. The main objective was to evaluate the performance of the gradient methods for measuring the O3 flux by comparing them with the EC O3 flux. In this study, turbulent exchange coefficients (K) calculated with three methods were compared. These methods were the aerodynamic gradient (AG) method (in which K is calculated by using wind speed and temperature gradients), the aerodynamic gradient combined with EC (AGEC) method, in which the friction velocity and other variables are based on EC measurements, and the modified Bowen ratio using the EC sensible heat flux and temperature gradient (MBR) method. Meanwhile, the effects of the measurement and calculation methods of the O3 concentration gradient were analyzed. The results showed that: (1) on average, the transfer coefficient computed by the MBR method was 40% lower, and the coefficient determined with the AG method was 25% higher, than that determined with the AGEC method. (2) The gradient method’s O3 fluxes with the MBR, AGEC, and AG methods were 30.4% lower, 11.7% higher, and 45.6% higher than the EC O3 flux, respectively. (3) The effect of asynchronous O3 concentration measurements on the O3 gradient must be eliminated when using one analyzer to cyclically measure two-level O3 concentrations. The accuracy of gradient methods for O3 flux is related to the exchange coefficient calculation method, and its precision mainly depends on the quality of the O3 gradient.

Fluxes of nitrogen oxides above a subtropical forest canopy in China.

Dry deposition of Nitrogen (N) in forests is commonly estimated from inferential method and/or throughfall measurements, with inevitable uncertainty. In this study, we applied an aerodynamic gradient method to directly measure the nitrogen oxides (NOx) flux above the canopy of a subtropical forest in southeastern China for two consecutive years. The flux and transfer velocity generally reached the maximum absolute values in the midday, with the largest diurnal maximum of absolute flux values observed in the winter of 2015 and that of transfer velocity in the autumn of 2015. The annual average transfer velocity was -0.79 and -0.38cms-1 in 2015 and 2016, respectively. Although the net downward NOx fluxes predominated for both years, upward flux (net emission) of NOx was observed during spring months, which reflected the possible bi-directional exchange balanced by soil-atmosphere and foliage-atmosphere exchanges. The NOx concentration seemed to be the most important factor controlling the NOx exchange above canopy, and could mainly explain the seasonal variation of N deposition. The linear regression between the NOx flux and concertation was explored, and it was observed that the deposition of NOx was offset by possible underlayer emission of NOx when the ambient NOx concentration below1.7 ppbv and 1.9 ppbv at night and in the day, respectively. The average dry deposition of NOx for the two years was 6.28±0.06kgNha-1 a-1, >40% of which might be uptake by the canopy, estimated by comparing the wet/throughfall deposition measurement of nitrate with the observation of NOx flux. This indicated the importance of stomatal uptake of NOx in nitrogen budget in subtropical forests.

Results of a comparative study of dry ozone deposition fluxes on grasslands and forest vegetation near Lake Baikal

The purpose of this work is the experimental study of the flux and rate of the dry deposition of ozone on different types of vegetation in the Baikal region. Based on the eddy covariance method and the flux gradient methods (including the aerodynamic gradient method (AGM), the modified Bowen method (MBR) and modified gradient method (MGM)) and with experimental data, the quantitative estimates of the fluxes and dry deposition velocity of ozone on the underlying surface were obtained for different environments (grasslands, forest).

Investigation of Transport and Transformation of Tropospheric Ozone in Terrestrial Ecosystems of the Coastal Zone of Lake Baikal

Forest ecosystems play an important role in the process of removing trace gases from the atmosphere. The purpose of this work is the experimental study of the flux and rate of the dry deposition of ozone on different types of vegetation in the Baikal region. Based on the eddy covariance method and the flux gradient methods (including the aerodynamic gradient method (AGM), the modified Bowen method (MBR) and modified gradient method (MGM)) and with experimental data, the quantitative estimates of the fluxes and dry deposition velocity of ozone on the underlying surface were obtained for different environments (grasslands, forest). The average values of the dry deposition velocity of ozone (Vd) were equal to 0.37 cm/s at night (0–3 h) and 0.91 cm/s during daytime hours (12–18 h). The ozone flux (F) was 0.24 μg m–2 s–1 at night and 0.72 μg m–2 s–1 in the afternoon. The quantitative estimates of Vd and F on vegetation and in the forest show a higher absorptive capacity of forests compared to soil vegetation.

Fluxes of Gaseous Elemental Mercury on a Mediterranean Coastal Grassland

Coastal rural areas can be a source of elemental mercury, but the potential influence of their topographic and climatic particularities on gaseous elemental mercury (GEM) fluxes have not been investigated extensively. In this study, gaseous elemental mercury was measured over Mediterranean coastal grassland located in Northern Greece from 2014 to 2015 and GEM fluxes were evaluated utilizing Monin–Obukhov similarity theory. The GEM fluxes ranged from –50.30 to 109.69 ng m−2 h−1 with a mean value equal to 10.50 ± 19.14 ng m−2 h−1. Concerning the peak events, with high positive and low negative GEM fluxes, those were recorded from the morning until the evening. Rain events were a strong contributing factor for enhanced GEM fluxes. The enhanced turbulent mixing under daytime unstable conditions led to greater evasion and positive GEM fluxes, while, during nighttime periods, the GEM evasion is lower, indicating the effect of atmospheric stability on GEM fluxes. The coastal grassland with its specific characteristics influences the GEM fluxes and this area could be characterized as a source of elemental mercury. This study is one of the rare efforts in the research community to estimate GEM fluxes in a coastal natural site based on aerodynamic gradient method.

Reducing the discrepancies between the Aerodynamic Gradient Method and other micrometeorological approaches for measuring fumigant emissions

Observations of fumigant and pesticide emissions are needed for multiple public health and environmental protection mandates. The aerodynamic gradient method (ADM) is commonly used to measure fumigant and pesticide emissions. However, the ADM may over estimate emissions compared to other micrometeorological and modeling approaches, which would increase uncertainty over the true flux estimate. Different studies with ADM have also used multiple differing transport functions that relate concentration gradients to emissions. Therefore, we tested different and more recent transport functions to try to correct the anticipated observed higher values with ADM using observations from two sites in California, USA. We evaluated different transport functions against eddy covariance observations and found that using the functions developed by Högström (1996) corrected the ADM values to be in line with other observational methods. For the Fresno experiment, cumulative emission masses from the ADM- Högström functions were within 7% of other approaches while the Pruitt function was >15% higher. Applying the Högström functions to a series of previous fumigation experiments in California saw reductions in the ADM observations of >25% for cumulative mass emissions. The results indicate that the Högström functions should be used for future ADM experiments in the absence of more robust transport factors for local meteorological conditions. The results also illustrate how previous ADM observations could be corrected to reduce uncertainty in flux emissions estimates.

Diurnal fluxes of HONO above a crop rotation

Abstract. Nitrous acid (HONO) fluxes were measured above an agricultural field site near Paris during different seasons. Above bare soil, different crops were measured using the aerodynamic gradient (AG) method. Two LOPAPs (LOng Path Absorption Photometer) were used to determine the HONO gradients between two heights. During daytime mainly positive HONO fluxes were observed, which showed strong correlation with the product of the NO2 concentration and the long wavelength UV light intensity, expressed by the photolysis frequency J(NO2). These results are consistent with HONO formation by photosensitized heterogeneous conversion of NO2 on soil surfaces as observed in recent laboratory studies. An additional influence of the soil temperature on the HONO flux can be explained by the temperature-dependent HONO adsorption on the soil surface. A parameterization of the HONO flux at this location with NO2 concentration, J(NO2), soil temperature and humidity fits reasonably well all flux observations at this location.

Application of an online ion-chromatography-based instrument for gradient flux measurements of speciated nitrogen and sulfur

Abstract. The dry component of total nitrogen and sulfur atmospheric deposition remains uncertain. The lack of measurements of sufficient chemical speciation and temporal extent make it difficult to develop accurate mass budgets and sufficient process level detail is not available to improve current air–surface exchange models. Over the past decade, significant advances have been made in the development of continuous air sampling measurement techniques, resulting with instruments of sufficient sensitivity and temporal resolution to directly quantify air–surface exchange of nitrogen and sulfur compounds. However, their applicability is generally restricted to only one or a few of the compounds within the deposition budget. Here, the performance of the Monitor for AeRosols and GAses in ambient air (MARGA 2S), a commercially available online ion-chromatography-based analyzer is characterized for the first time as applied for air–surface exchange measurements of HNO3, NH3, NH4+, NO3−, SO2 and SO42−. Analytical accuracy and precision are assessed under field conditions. Chemical concentrations gradient precision are determined at the same sampling site. Flux uncertainty measured by the aerodynamic gradient method is determined for a representative 3-week period in fall 2012 over a grass field. Analytical precision and chemical concentration gradient precision were found to compare favorably in comparison to previous studies. During the 3-week period, percentages of hourly chemical concentration gradients greater than the corresponding chemical concentration gradient detection limit were 86, 42, 82, 73, 74 and 69 % for NH3, NH4+, HNO3, NO3−, SO2 and SO42−, respectively. As expected, percentages were lowest for aerosol species, owing to their relatively low deposition velocities and correspondingly smaller gradients relative to gas phase species. Relative hourly median flux uncertainties were 31, 121, 42, 43, 67 and 56 % for NH3, NH4+, HNO3, NO3−, SO2 and SO42−, respectively. Flux uncertainty is dominated by uncertainty in the chemical concentrations gradients during the day but uncertainty in the chemical concentration gradients and transfer velocity are of the same order at night. Results show the instrument is sufficiently precise for flux gradient applications.

A comparison of measured HONO uptake and release with calculated source strengths in a heterogeneous forest environment

Abstract. Vertical mixing ratio profiles of nitrous acid (HONO) were measured in a clearing and on the forest floor in a rural forest environment. For the forest floor, HONO was found to predominantly deposit, whereas for the clearing, net deposition dominated only during nighttime and net emissions were observed during daytime. For selected days, net fluxes of HONO were calculated from the measured profiles using the aerodynamic gradient method. The emission fluxes were in the range of 0.02 to 0.07 nmol m−2 s−1 and thus were in the lower range of previous observations. These fluxes were compared to the strengths of postulated HONO sources. Laboratory measurements of different soil samples from both sites revealed an upper limit for soil biogenic HONO emission fluxes of 0.025 nmol m−2 s−1. HONO formation by light-induced NO2 conversion was calculated to be below 0.03 nmol m−2 s−1 for the investigated days, which is comparable to the potential soil fluxes. Due to light saturation at low irradiance, this reaction pathway was largely found to be independent of light intensity, i.e. it was only dependent on ambient NO2. We used three different approaches based on measured leaf nitrate loadings for calculating HONO formation from HNO3 photolysis. While the first two approaches based on empirical HONO formation rates yielded values in the same order of magnitude as the estimated fluxes, the third approach based on available kinetic data of the postulated pathway failed to produce noticeable amounts of HONO. Estimates based on reported cross sections of adsorbed HNO3 indicate that the lifetime of adsorbed HNO3 was only about 15 min, which would imply a substantial renoxification. Although the photolysis of HNO3 was significantly enhanced at the surface, the subsequent light-induced conversion of the photolysis product NO2 did not produce considerable amounts of HONO. Consequently, this reaction might occur via an alternative mechanism. By explicitly calculating HONO formation based on available kinetic data and simple parameterizations, we showed that (a) for low NOx the light-induced conversion of NO2 on humic acids is already light saturated by the early morning, (b) HONO formation from photolysis of adsorbed HNO3 appears to proceed via an alternative mechanism and (c) estimates of HONO emissions from soil are very sensitive to mass transfer and acidic soils do not necessarily favour HONO emissions.

A modified micrometeorological gradient method for estimating O<sub>3</sub> dry depositions over a forest canopy

Abstract. Small pollutant concentration gradients between levels above a plant canopy result in large uncertainties in estimated air–surface exchange fluxes when using existing micrometeorological gradient methods, including the aerodynamic gradient method (AGM) and the modified Bowen ratio method (MBR). A modified micrometeorological gradient method (MGM) is proposed in this study for estimating O3 dry deposition fluxes over a forest canopy using concentration gradients between a level above and a level below the canopy top, taking advantage of relatively large gradients between these levels due to significant pollutant uptake in the top layers of the canopy. The new method is compared with the AGM and MBR methods and is also evaluated using eddy-covariance (EC) flux measurements collected at the Harvard Forest Environmental Measurement Site, Massachusetts, during 1993–2000. All three gradient methods (AGM, MBR, and MGM) produced similar diurnal cycles of O3 dry deposition velocity (Vd(O3)) to the EC measurements, with the MGM method being the closest in magnitude to the EC measurements. The multi-year average Vd(O3) differed significantly between these methods, with the AGM, MBR, and MGM method being 2.28, 1.45, and 1.18 times that of the EC, respectively. Sensitivity experiments identified several input parameters for the MGM method as first-order parameters that affect the estimated Vd(O3). A 10% uncertainty in the wind speed attenuation coefficient or canopy displacement height can cause about 10% uncertainty in the estimated Vd(O3). An unrealistic leaf area density vertical profile can cause an uncertainty of a factor of 2.0 in the estimated Vd(O3). Other input parameters or formulas for stability functions only caused an uncertainly of a few percent. The new method provides an alternative approach to monitoring/estimating long-term deposition fluxes of similar pollutants over tall canopies.

Mercury vapor air–surface exchange measured by collocated micrometeorological and enclosure methods – Part II: Bias and uncertainty analysis

Abstract. Dynamic flux chambers (DFCs) and micrometeorological (MM) methods are extensively deployed for gauging air–surface Hg0 gas exchange. However, a systematic evaluation of the precision of the contemporary Hg0 flux quantification methods is not available. In this study, the uncertainty in Hg0 flux measured by the relaxed eddy accumulation (REA) method, the aerodynamic gradient method (AGM), the modified Bowen ratio (MBR) method, as well as DFC of traditional (TDFC) and novel (NDFC) designs, are assessed using a robust data set from two field intercomparison campaigns. The absolute precision in Hg0 concentration difference (ΔC) measurements is estimated at 0.064 ng m−3 for the gradient-based MBR and AGM systems. For the REA system, the parameter is Hg0 concentration (C) dependent at 0.069 + 0.022C. During the campaigns, 57 and 62 % of the individual vertical gradient measurements are found to be significantly different from 0, while for the REA technique, the percentage of significant observations is lower. For the chambers, non-significant fluxes are confined to a few night-time periods with varying ambient Hg$^{0}$ concentrations. Relative bias for DFC-derived fluxes is estimated to be ~ ±10, and ~ 85% of the flux bias is within ±2 ng m−2 h−1 in absolute terms. The DFC flux bias follows a diurnal cycle, which is largely affected by the forced temperature and irradiation bias in the chambers. Due to contrasting prevailing micrometeorological conditions, the relative uncertainty (median) in turbulent exchange parameters differs by nearly a factor of 2 between the campaigns, while that in ΔC measurement is fairly consistent. The estimated flux uncertainties for the triad of MM techniques are 16–27, 12–23 and 19–31% (interquartile range) for the AGM, MBR and REA methods, respectively. This study indicates that flux-gradient-based techniques (MBR and AGM) are preferable to REA in quantifying Hg0 flux over ecosystems with low vegetation height. A limitation of all Hg0 flux measurement systems investigated is their inability to obtain synchronous samples for the calculation of ΔC. This reduces the precision of flux quantification, particularly in the MM systems under non-stationarity of ambient Hg0 concentration. For future applications, it is recommended to accomplish ΔC derivation from simultaneous collected samples.

English

The aerodynamic gradient method was applied to estimate dry deposition flux of SO2 over dry deciduous forest in Nakorn Ratchasima province, Thailand. The meteorological parameters and concentrations of SO2 were measured in real time for one year on the experimental tower at 36 and 27 m high. The flux observed in the wet season were found two times higher than the value observed in the dry seasons, i.e. 20±7.58 and 10±11.05 ng m-2 s-1, respectively. The leaf area index and the ambient humidity were believed to assert the rate of SO2 deposition. The average friction velocities were estimated to be 0.26±0.02 and 0.48±0.06 m s–¹, for the dry and the wet season, respectively. The friction velocity was very much depended on the surface roughness of the forest canopy. The Vd of SO2 evaluated by the aerodynamic gradient was compared with Vd calculated by the resistance model. It was found that the observed Vd was in close proximity with the model prediction in daytime in all conditions, i.e. wet, dry and annual average. The annual average Vd determined by the Aerodynamic gradient was 0.43±0.06 cm s-1.