基于可调谐吸收光谱的畜禽舍氨气浓度检测

为开发一种基于可调谐吸收光谱（Tunable Diode Laser Absorption Spectroscopy,TDLAS）技术的畜禽舍NH3浓度实时在线监测装置,以满足畜禽舍环境监测与控制的需要。该研究基于TDLAS技术,采用气室式封闭光程,搭建了一套畜禽舍NH3浓度检测系统。该系统采用波长为1 512 nm蝶形激光器作为光源,根据分子吸收光谱理论,采用波长调制技术,实现了对畜禽舍NH3浓度检测。为优化检测系统性能,通过改变锯齿扫描信号、调制正弦信号的幅值与频率以及输入信号与参考信号相位差,确定了系统最佳的调制参数,并通过系统优化试验确定了系统最佳的气室加热温度、系统响应时间与二次谐波平均次数等关键参数。最后,通过浓度标定试验与性能试验对检测系统进行了测试。试验结果表明,检测系统调制参数在正弦调制信号频率为9 kHz、正弦调制信号幅值为30 mV、锯齿扫描信号频率为1 Hz、锯齿扫描范围为170～215 mV、谐波分析中输入信号与参考信号相位差为50°参数下对应的二次谐波形状与幅值最佳;不同浓度NH3与二次谐波幅值之间具有良好的线性关系（拟合方程相关系数r=0.995 8）;检测系统的进气响应时间约为42 s（气室自充气达到目标浓度99%）;气室加热温度为403 K时,NH3在气室吸附作用最小;Allan方差分析表明,检测系统在积分时间为10 s时达到探测限,探测限为0.038 mg/m3。在最优系统参数下对系统进行性能试验,得到检测系统综合线性误差为1.00%,定量测量综合重复误差为0.51％,可满足畜禽舍内NH3浓度长期持续监测的需求。     

Comparison of RADM dry deposition algorithms with a site-specific method for inferring dry deposition

Data collected during 1986 at seven widely separated sites in the eastern United States were used to estimate weekly averages of deposition velocities for SO₂, O₃, HNO₃, and SO _inf4 ^sup2? with both a modified version of the RADM dry deposition module and a site-specific inferential technique developed by the Atmospheric Turbulence and Diffusion Division of the National Oceanic and Atmospheric Administration's Air Resources Laboratory. The results show some systematic differences between the two techniques, even when the module uses distributions of landuse types that match as closely as possible the observed vegetation coverages used in the inferential technique. When one ignores the systematic differences that easily could be removed by minor changes in the algorithms for computing resistances to deposition, weekly averages of the deposition velocities calculated with the two methods are within approximately ±30% of each other for SO₂ and O₃. Overall, the relative differences in the deposition velocities for HNO₃ and SO _inf4 ^sup2? are about ±30 and ±50%, respectively. Use of the module with landuse types extrapolated to areas as large as RADM grid cells (approximately 80 km square) around the measurement stations produces weekly averages within ±20% of the site-specific estimates for SO₂, O₃, and SO _inf4 ^sup2? and approximately ±30% for HNO₃ if one avoids landuse types such as urban and water areas that are both nonrepresentative and have very different characteristics from the measurement sites. These estimates are not complete measures of the true uncertainty associated with the two techniques because they do not account for such effects as differences in the siting of instrumentation for collecting input data and the inability of the computational algorithms to include the many surface nonuniformities that typically exist in the areas surrounding measurement sites.     

Ambient levels and dry deposition fluxes of mercury to Lakes Huron,Erie and St. Clair

Ambient concentrations and dry deposition fluxes of Hg in the gas and particle phase to Lakes St. Clair, Erie and Huron were estimated with a hybrid receptor-deposition model (HRD). The ambient gas and particulate phase Hg concentrations were predicted to vary by a factor of 12 to 18 during the transport of air masses traversing the lakes. The ensemble average deposition fluxes of fine particle Hg ranged from 7 pg/m²-h to 15.3 pg/m²-h over Lake St. Clair, 0.5 to 4.2 pg/m²-h over Lake Huron and 5.1 to 20.6 pg/m²-h over Lake Erie. The deposition flux of coarse particle Hg was in the range of 50 to 84 pg/m²-h over Lake St. Clair, 4.7 to 24.2 pg/m²-h over Lake Huron and 5.1 to 20.6 pg/m²-h over Lake Erie. Gaseous Hg volatilized at a rate of 0.21 to 0.52 ng/m²-h from Lake Huron and 0.13 to 0.36 from Lake Erie. Gas phase Hg was deposited at a rate of 5.9 ng/m²-h and/or volatilized at a rate of 0.5 ng/m²-h from Lake St. Clair depending upon the location of the sampling site used in the HRD model. The effect of meteorological conditions, particle size distributions and type and location of the sampling sites played an important role in the transfer of atmospheric Hg to and/or from the lakes.     

Dry deposition measurements using water as a receptor: A chemical approach

The field measurement of dry deposition still represents a difficult task. In our approach, a 1 to 2 cm thick layer of water in a petri dish with a diameter of 22 cm, serves as a surrogate surface. The atmospheric constituents taken up by the water can be analyzed chemically by the same procedure as for the wet deposition samples. In contrast to solid surrogate surfaces, water exhibits the following advantageous properties: low and constant surface resistance, high sticking coefficient for aerosols, and predictable Sorption behavior for gases. Consequently, the deposition rates measured to the wet surface are generally higher, by up to a factor of 4 for NH₄ ⁺, Cl^?, NO₃ ^? and SO₄ ^2?, than those to a dry surface, but still smaller than the concurrent wet deposition rates. We observed the following average dry deposition rates in μmol m^?2 d^?1∶ NH₄ ⁺ 48.3, Ca²⁺ 40.7, Na⁺ 15.8, Mg²⁺ 8.4, K⁺ 4.2, H-Aci 36.4; SO₄ ^2? 57.2, Cl^? 39.2, NO₃ ^? 34.5, HSO₃ ^? 5.7, formate 4.0; acid soluble metals: Fe 2.8, Zn 0.60, Cu 0.11, Pb 0.073, Cd 0.0022. The soluble fraction of Zn, Cd, Cu, Pb and Fe in the dry deposition varied with the pH of the water phase corresponding to the adsorption tendency of these metals to oxide surfaces. The sampling method also allows tracing of regionally and locally emitted atmospheric pollutants. In our study the local pollution sources included road salting, construction work and a refuse incinerator. Finally, chemical reactions occurring in the atmosphere, such as the conversion of Cl^? to HCl by HNO₃ or the oxidation of SO₂, can be identified by evaluating the data. The method proposed is relevant to measure reproducibly the dry deposition of a variety of compounds to water bodies and moist vegetation.     

The calculation of transboundary and deposition fluxes of SO2 and sulfate by means of aircraft measurements

Aircraft measurements of the air pollutants SO₂ and sulfate (SO_x is defined as SO₂ plus sulfate), plus data on wind velocity, wind direction and depth of the planetary boundary layer, enable the calculation of transboundary mass fluxes of SO_x. When emission data are available, an emission-deposition balance of SO_x can be determined. The results of a measurement flight, carried out on 12 February, 1986, are presented. Two tracks were flown, along the eastern and along the western border of the Netherlands, respectively. The wind was easterly. The calculated deposition flux of SO_x is converted to an area-averaged dry deposition velocity (ν _d ). The result, ν _d = 1.2 × 10^?2 m s^?1, seems to be in good agreement with literature data.     

An improved method for measuring soil N2O fluxes using a quantum cascade laser with a dynamic chamber

A dynamic chamber method was developed to measure fluxes of N₂O from soils with greater accuracy than previously possible, through the use of a quantum cascade laser (QCL). The dynamic method was compared with the conventional static chamber method, where samples are analysed subsequently on a gas chromatograph. Results suggest that the dynamic method is capable of measuring soil N₂O fluxes with an uncertainty of typically less than 1–2 µg N₂O‐N m^?2 hour^?1 (0.24–0.48 g N₂O‐N ha^?1 day^?1), much less than the conventional static chamber method, because of the greater precision and temporal resolution of the QCL. The continuous record of N₂O and CO₂ concentration at 1 Hz during chamber closure provides an insight into the effects that enclosure time and the use of different regression methods may introduce when employed with static chamber systems similar in design. Results suggest that long enclosure times can contribute significantly to uncertainty in chamber flux measurements. Non‐linear models are less influenced by effects of long enclosure time, but even these do not always adequately describe the observed concentrations when enclosure time exceeds 10 minutes, especially with large fluxes.     

Measurements of wet and dry deposition in a Northern Hardwood forest

Inputs of wet and dry deposition were monitored at the Huntington Forest in the Adirondack Mountains of New York for two years in the open and beneath the canopy of a northern hardwood forest. In the open, ion flux estimates were similar using wet-only weekly (NADP protocol) and event collections, but bulk collections were higher for all ions except H⁺, which was much lower. These differences were due to the contribution of dry deposition and possible biotic alterations in bulk collectors. Dry deposition was estimated using air concentrations and ion-specific depositional velocities modeled with meteorological data, and contributed substantially to the input of all ions [H⁺ (45%), Na⁺ (24%), K⁺ (22%), NH₄ ⁺ (12%), Ca²⁺ (58%), Mg²⁺(43%), NO₃ ^? (55%), Cl^? (27%) and SO₄ ^?2 (26%)]. Dry input of base cations was dominated by coarse particles, whereas gaseous inputs were more important for S and NO₃ ^?. Atmospheric concentrations of SO₂ and inputs of SO₄ ^2? and H⁺ were lower at this site than sites closer to point sources of S gas emission. The importance of estimating atmospheric inputs was examined using examples of elemental budgets. For example, different estimates of the contribution of dry deposition of SO₄ ^2? (9–21 meq m^?2 y^?1) resulted in conclusions ranging from no net retention to a net loss of this element. Such differences have important implications in assessing the current and future role of atmospheric inputs in affecting elemental cycling.     

The dry deposition of gaseous and participate nitrogen compounds to a spruce stand

The dry deposition of particle-bound NH₄ ⁺ and NO₃ ^– and of gaseous NH₃ and HNO₃ to a 45 year old Norway Spruce forest was determined by the inferential method. Deposition velocities were calculated from meteorological data and plant morphology by a multi-layer model which combines the transfer of the trace substances within the canopy and their absorption probabilities due to a variety of deposition mechanisms. For gaseous deposition the same mathematical concept was adopted as for particles. That means that this approach is an alternative to the common concept of resistance analogy. The mean deposition velocities found were 0.47 cm s^–1 for NH₄ ⁺ and 1.85 cm s^–1 for NO₃ ^–. While these values are in the range found in other studies, the mean deposition velocities for the gases were quite large. For NH₃ 13 cm s^–1 were found and for HNO₃ 11 cm s^–1. It is suggested that the absorption of these gases on the plant surfaces is not as effective as assumed in the model.     

Soil acidification and element fluxes of a Fagus sylvatica forest as influenced by simulated nitrogen deposition

Water, Air, &; Soil Pollution - The influence of simulated 3- and 9-fold increases in the current N deposition on element fluxes and soil acidification was investigated in a beech forest in S...     

Measured values of the dry deposition velocities of atmospheric aerosols carrying natural and fallout radionuclides using artificial collectors

The dry deposition velocitiesVg of aerosols carrying (a) fallout beta activity from nuclear tests, (b) natural radioactivity due to thoron daughter²¹²Ph (Th-B) and (c) cosmic-ray produced⁷Be have been measured in Bombay, India, using artificial collectors consisting of trays with a thin layer of water to retain the deposited material. The location of Bombay is eminently suitable for such measurements in view of the existence of a long dry period of several months without any rainfall. The measuredVg values (cm s^?1)) are 0.063 ± 0.06 (1 S.D.) for fallout beta activity from 900 daily readings, 0.033 ± 0.03 (1 S.D.) for²¹²Pb from 80 daily measurements and 0.023 ± 0.014 (1 S.D.) for⁷Be from 23 bi-monthly measurements. A study of the associated meteorological parameters showed some correlation with wind velocity only in the case of radioactive fallout.     

In situ quantification of CH<Subscript>4</Subscript> bubbling events from a peat soil using a new infrared laser spectrometer

Purpose  

CH₄ emissions from peatlands are space and time dependent. The variety of efflux routes contributes to these variabilities. CH₄ bubbling remains difficult to investigate since it occurs on a timescale of seconds. The aims of this study were to use for the first time the recently built infrared high-resolution spectrometer, SPectrometre Infra-Rouge In situ Troposphérique to (1) measure in situ CH₄ fluxes in natural and artificial peatland plot and (2) observe online bubbling events with quantification of CH₄ emission fluxes corresponding to this very sudden degassing event.     

Long term effects of enhanced nitrogen deposition on a lowland dry heath in southern Britain

Experimental additions of ammonium sulphate to a nitrogen-poor dry heathland have been carried out since 1989. There are four nitrogen treatments: a control (receiving artificial rain only), a low treatment which receives an additional 7.7 kg N ha^?1 yr^?1, a high treatment receiving 15.4 kg N ha^?1 yr^?1 and an alternating treatment which receives either the control or the high nitrogen additions, in alternate years. The estimated background deposition at the study site is 13–18 kg N ha^?1 yr^?1, a value similar to the critical load that has been suggested for the conversion of lowland heath to grassland. Over the past 5 years there have been significant stimulations in shoot growth, flowering, canopy density and litter production. Flowering, in particular, strongly reflects nitrogen additions in the alternating treatment. Current models of the response of dry Calluna heathlaud to enhanced nitrogen deposition suggest that higher tissue nitrogen levels will occur and will be accompanied by heightened sensitivity to secondary stresses. This may in turn lead to canopy breakdown and replacement by grassland. The application of nitrogen at deposition rates only slightly in excess of the critical load over five years has produced small, non-significant increases in shoot nitrogen content. However, there is clear evidence of a large positive effect on shoot growth, flowering, litter production and canopy density of Calluna. The observation of these responses at the application rates used in this study supports the current proposals for critical loads of nitrogen for lowland heaths.     

A comparison of regression methods for estimating soil-atmosphere diffusion gas fluxes by a closed-chamber technique

Continuous changes in methane (CH₄) and carbon dioxide (CO₂) concentrations inside a closed chamber were measured on the forest floor at three sites: a deciduous forest and a coniferous forest in Hokkaido, Japan, and a birch forest in West Siberia, Russian Federation. Flux estimations by three types of regression methods, exponential, nonlinear, and linear, were examined using field-collected concentration data. The pattern of change with time of the gas concentration in the headspace differed, mainly according to site but also, to a lesser extent, according to the gas. This was a function of both the chamber height and surface soil property relating to soil gas diffusion and the gas concentration profile. Flux estimations did not differ statistically between the exponential and nonlinear methods for either gas at any site, because both of those regression methods were based on diffusion theory. However, the flux values estimated by linear regression were significantly different from those estimated by the other two methods for both CH₄ and CO₂ at the deciduous forest site and for CO₂ at the coniferous forest site. Shortening the chamber deployment period improved the linearity of the curve, but did not completely eliminate the error. Our results suggest that linear regression is not a good model of the change in headspace concentration with time.     

Design and initial tests of a dynamic enclosure chamber for measurements of vapor-phase mercury fluxes over soils

In an effort to establish reliable methodologies for measuring fluxes of mercury (Hg) across the soil-air interface, we have developed a field flux chamber built with FEP Teflon. To evaluate our field flux chamber system, a series of laboratory and field tests were performed. The observations of relatively low chamber blanks and low blank-to-sample ratios for the FEP Teflon chamber suggest its potential in Hg flux investigations. Despite its potential, Hg exchange rate measurements using the field flux chamber method must be made with great caution since it can be subject to contamination problems associated with the selection of chamber materials.     

Effect of wetting intensity on soil GHG fluxes and microbial biomass under a temperate forest floor during dry season

The increasing frequency of periodic droughts followed by heavy rainfalls is expected for this current century, but little is known about the effects of wetting intensity on the in situ biogenic greenhouse gas (GHG) fluxes of forest soils and soil microbial biomass. To gain new insights into the underlying mechanisms responsible for wetting-induced GHG fluxes in situ, rain simulation field experiments during a natural prolonged drought period were done under a temperate forest in northeast China. The intensity of rainfall-induced CO₂ pulses increased from 0.84 to 2.08 g CO₂–C m^? 2 d^? 1 with the intensity of wetting up to ca. 80% water-filled pore space, which coincided with an increase in soil microbial biomass and with a decrease in soil labile organic C following wetting. Methane uptake rates decreased from 1.76 to 0.87 mg CH₄–C m^? 2 d^? 1 with the intensity of wetting. Wetting dry forest floor increased N₂O fluxes from 6.2 to 25.9 μg N₂O–N m^? 2 d^? 1, but there was no significant difference between all experimental wetted plots. The rainfall-induced N₂O pulses with increasing wetting intensity were opposite to that of the CO₂ pulses, showing a maximum response at the lowest wetting intensity. An analysis of the temperature sensitivity of GHG fluxes indicated that temperature had an increased effect on the in situ CO₂ flux and CH₄ uptake, respectively, under wetted and dry conditions. The global warming potential of GHG fluxes and Q₁₀ value of the temperature response of CO₂ fluxes increased linearly with wetting intensity. The results indicate that the rainfall-induced soil CO₂ pulse is mainly due to enhanced microbial consumption on substrates and highlight the complex nature of belowground C-cycling responses to climate change in northeast China forests that normally experience periodic droughts followed by heavy rainfalls over the year.     

Simultaneous stopped-flow determination of butylated hydroxyanisole and propyl gallate using a T-format luminescence spectrometer

A simple and fast luminescent method is used for the first time to resolve a mixture of two synthetic antioxidants, propyl gallate (PG) and butylated hydroxyanisole (BHA), by the joint use of the stopped-flow mixing technique and a T-format luminescence spectrometer. The determination of these compounds involves two different and independent reactions. On the one hand, PG determination is based on an energy transfer process that involves the formation of a lanthanide chelate with terbium in the presence of Triton X-100 and tri-n-octylphosphine oxide. On the other hand, BHA is determined using a reaction between the oxidized form of Nile Blue and the antioxidant. Both systems are excited at the same excitation wavelength (310 nm), and the emission wavelengths are 545 and 665 nm for PG and BHA, respectively. The absence of overlap in the emission spectra makes it possible to measure separately the analytes in each channel of the instrument. Initial rate and equilibrium signal are used as analytical parameters and measured in 0.1 and 1 s for PG and BHA, respectively. Calibration graphs are linear over the range 0.09-3.5 microg mL(-)(1) for PG and 0.3-15 microg mL(-)(1) for BHA. The relative standard deviations of both systems are close to 2%. The proposed method is applied to the determination of these two antioxidants in several commercial food samples with recoveries ranging between 94.8 and 102.9% for PG and between 94.1 and 102.1% for BHA.     

Correcting for underlying absorption interferences in Fourier transform infrared trans analysis of edible oils using two-dimensional correlation techniques

Substantive improvement in the sensitivity of the AOAC/AOCS spectral ratioing method for the determination of isolated trans isomers in edible oils was recently achieved by the application of a new spectral reconstitution (SR) technique that facilitates the FTIR analysis of edible oils in the transmission mode. However, the general applicability of the spectral ratioing method is still severely limited by the requirement to know the provenance of the oil to be analyzed and have on hand its trans-free counterpart so that the underlying triacylglycerol absorptions in the trans measurement region (990-945 cm(-1)), henceforth referred to as UAt , may be ratioed out. To eliminate the need for a trans-free reference oil, we have employed two-dimensional (2D) correlation spectroscopy to search for other spectral features that might correlate with and serve to estimate the UAt . The three-dimensional contour maps obtained by 2D correlation analysis of the spectra of 10 trans-free oils of different oil types, recorded using the SR procedure, revealed such correlations in two spectral regions, 1700-1600 and 4500-4300 cm(-1), exhibiting one maximum and two maxima, respectively, with wavenumber coordinates of (968, 4407), (968, 4299), and (968, 1650). The latter two correlations, when optimized, produced excellent linear regression relationships (r>0.95) with the UAt . The spectra of five sets of trielaidin-spiked oils were corrected for the UA t using these relationships, and their trans contents were predicted from the calibration equation generated for the spectral ratioing procedure. Linear regression of predicted versus added trans over the range of 0-1.6% trans, which is below the limit of quantitation of the AOAC/AOCS spectral ratioing method, yielded r=0.88-0.90 with an SD of approximately 0.2% trans. These results indicate that the combination of the SR technique with the UA t correction approach may provide a simple and accurate FTIR method for the analysis of the trans content of fats and oils that would be competitive with GC.     

Estimation of wet and dry deposition of pollutant sulfur in eastern Canada as a function of major source regions

The contributions of major anthropogenic source regions to wet and dry deposition of total S in eastern Canada are estimated for a winter month and a summer month with the ASTRAP model. Results indicate that the U.S. and Canada contribute approximately equal amounts to total S deposition in Canada; Canadian sources contribute more than one half of dry deposition and less than one half of wet deposition.