Effect of sampling frequency on estimates of cumulative nitrous oxide emissions

It is generally recognized that soil N(2)O emissions can exhibit pronounced day-to-day variations; however, measurements of soil N(2)O flux with soil chambers typically are done only at discrete points in time. This study evaluated the impact of sampling frequency on the precision of cumulative N(2)O flux estimates calculated from field measurements. Automated chambers were deployed in a corn/soybean field and used to measure soil N(2)O fluxes every 6 h from 25 Feb. 2006 through 11 Oct. 2006. The chambers were located in two positions relative to the fertilizer bands-directly over a band or between fertilizer bands. Sampling frequency effects on cumulative N(2)O-N flux estimation were assessed using a jackknife technique where populations of N(2)O fluxes were constructed from the average daily fluxes measured in each chamber. These test populations were generated by selecting measured flux values at regular time intervals ranging from 1 to 21 d. It was observed that as sampling interval increased from 7 to 21 d, variances associated with cumulative flux estimates increased. At relatively frequent sampling intensities (i.e., once every 3 d) N(2)O-N flux estimates were within +/-10% of the expected value at both sampling positions. As the time interval between sampling was increased, the deviation in estimated cumulative N(2)O flux increased, such that sampling once every 21 d yielded estimates within +60% and -40% of the actual cumulative N(2)O flux. The variance of potential fluxes associated with the between-band positions was less than the over-band position, indicating that the underlying temporal variability impacts the efficacy of a given sampling protocol.     

Chemical evaluation of odor reduction by soil injection of animal manure

Field application of animal manure is a major cause of odor nuisance in the local environment. Therefore, there is a need for methods for measuring the effect of technologies for reducing odor after manure application. In this work, chemical methods were used to identify key odorants from field application of pig manure based on experiments with surface application by trailing hoses and soil injection. Results from three consecutive years of field trials with full-scale equipment are reported. Methods applied were: membrane inlet mass spectrometry (MIMS), proton-transfer-reaction mass spectrometry (PTR-MS), gold-film hydrogen sulfide (H?S) detection, all performed on site, and thermal desorption gas chromatography with mass spectrometry (TD-GC/MS) based on laboratory analyses of field samples. Samples were collected from a static flux chamber often used for obtaining samples for dynamic olfactometry. While all methods were capable of detecting relevant odorants, PTR-MS gave the most comprehensive results. Based on odor threshold values, 4-methylphenol, H?S, and methanethiol are suggested as key odorants. Significant odorant reductions by soil injection were consistently observed in all trials. The flux chamber technique was demonstrated to be associated with critical errors due to compound instabilities in the chamber. This was most apparent for H?S, on a time scale of a few minutes, and on a longer time scale for methanethiol.     

Design and performance of a dynaniic gas flux chamber

Chambers are commonly used to measure the emission of many trace gases and chemicals from soil. An aerodynamic (flow through) chamber was designed and fabricated to accurately measure the surface flux of trace gases. Flow through the chamber was controlled with a small vacuum at the outlet. Due to the design using fans, a partition plate, and aerodynamic ends, air is forced to sweep parallel and uniform over the entire soil surface. A fraction of the air flowing inside the chamber is sampled in the outlet. The air velocity inside the chamber is controlled by fan speed and outlet suction flow rate. The chamber design resulted in a uniform distribution of air velocity at the soil surface. Steady state flux was attained within 5 min when the outlet air suction rate was 20 L/min or higher. For expected flux rates, the presence of the chamber did not affect the measured fluxes at outlet suction rates of around 20 L/min, except that the chamber caused some cooling of the surface in field experiments. Sensitive measurements of the pressure deficit across the soil layer in conjunction with measured fluxes in the source box and chamber outlet show that the outflow rate must be controlled carefully to minimize errors in the flux measurements. Both over- and underestimation of the fluxes are possible if the outlet flow rate is not controlled carefully. For this design, the chamber accurately measured steady flux at outlet air suction rates of approximately 20 L/min when the pressure deficit within the chamber with respect to the ambient atmosphere ranged between 0.46 and 0.79 Pa.     

Nitrous oxide emissions from corn-soybean systems in the midwest

Soil N2O emissions from three corn (Zea mays L.)-soybean [Glycine max (L.) Merr.] systems in central Iowa were measured from the spring of 2003 through February 2005. The three managements systems evaluated were full-width tillage (fall chisel plow, spring disk), no-till, and no-till with a rye (Secale cereale L. 'Rymin') winter cover crop. Four replicate plots of each treatment were established within each crop of the rotation and both crops were present in each of the two growing seasons. Nitrous oxide fluxes were measured weekly during the periods of April through October, biweekly during March and November, and monthly in December, January, and February. Two polyvinyl chloride rings (30-cm diameter) were installed in each plot (in and between plant rows) and were used to support soil chambers during the gas flux measurements. Flux measurements were performed by placing vented chambers on the rings and collecting gas samples 0, 15, 30, and 45 min following chamber deployment. Nitrous oxide fluxes were computed from the change in N2O concentration with time, after accounting for diffusional constraints. We observed no significant tillage or cover crop effects on N2O flux in either year. In 2003 mean N2O fluxes were 2.7, 2.2, and 2.3 kg N2O-N ha(-1) yr(-1) from the soybean plots under chisel plow, no-till, and no-till + cover crop, respectively. Emissions from the chisel plow, no-till, and no-till + cover crop plots planted to corn averaged 10.2, 7.9, and 7.6 kg N2O-N ha(-1) yr(-1), respectively. In 2004 fluxes from both crops were higher than in 2003, but fluxes did not differ among the management systems. Fluxes from the corn plots were significantly higher than from the soybean plots in both years. Comparison of our results with estimates calculated using the Intergovernmental Panel on Climate Change default emission factor of 0.0125 indicate that the estimated fluxes underestimate measured emissions by a factor of 3 at our sites.     

Importance of Sediment–Water Interactions in Coeur d’Alene Lake,Idaho, USA: Management Implications

A field study at Coeur dAlene Lake, Idaho, USA, was conducted between October 1998 and August 2001 to examine the potential importance of sediment–water interactions on contaminant transport and to provide the first direct measurements of the benthic flux of dissolved solutes of environmental concern in this lake. Because of potential ecological effects, dissolved zinc and orthophosphate were the solutes of primary interest. Results from deployments of an in situ flux chamber indicated that benthic fluxes of dissolved Zn and orthophosphate were comparable in magnitude to riverine inputs. Tracer analyses and benthic-community metrics provided evidence that solute benthic flux were diffusion-controlled at the flux-chamber deployment sites. That is, effects of biomixing (or bioturbation) and ground-water interactions did not strongly influence benthic flux. Remediation efforts in the river might not produce desired water-quality effects in the lake because imposed shifts in concentration gradients near the sediment–water interface would generate a benthic feedback response. Therefore, development of water-quality models to justify remediation strategies requires consideration of contaminant flux between the water column and underlying sediment in basins that have been affected by long-term (decadal) anthropogenic activities.     

Passive flux meter measurement of water and nutrient flux in saturated porous media: bench-scale laboratory tests

The passive nutrient flux meter (PNFM) is introduced for simultaneous measurement of both water and nutrient flux through saturated porous media. The PNFM comprises a porous sorbent pre-equilibrated with a suite of alcohol tracers, which have different partitioning coefficients. Water flux was estimated based on the loss of loaded resident tracers during deployment, while nutrient flux was quantified based on the nutrient solute mass captured on the sorbent. An anionic resin, Lewatit 6328 A, was used as a permeable sorbent and phosphate (PO4(3-)) was the nutrient studied. The phosphate sorption capacity of the resin was measured in batch equilibration tests as 56 mg PO4(3-) g(-1), which was determined to be adequate capacity to retain PO4(3-) loads intercepted over typical PNFM deployment periods in most natural systems. The PNFM design was validated with bench-scale laboratory tests for a range of 9.8 to 28.3 cm d(-1) Darcy velocities and 6 to 43 h deployment durations. Nutrient and water fluxes measured by the PNFM averaged within 6 and 12% of the applied values, respectively, indicating that the PNFM shows promise as a tool for simultaneous measurement of water and nutrient fluxes.     

On-line greenhouse gas detection from soils and rock formations

Several on-site studies have been conducted on rock formations and soils where gases were collected into boreholes. The equipment consisted of packers isolating a chamber for gas collection. A pump allows gas transfer towards FT-IR sensors located at the surface. Such analytical approach shows several advantages for gas monitoring in boreholes: it allows variation detection with time of the partial pressure of gases; detection and evolution with time of the concentration of annex gases or markers; application to the injection and post-injection periods to determine possible deviations from a previously recorded baseline; and possible use of several boreholes in networks.     

Nitrous oxide,nitric oxide,and nitrogen dioxide fluxes from soils after manure and urea application

Nitrous oxide is a greenhouse gas, and NO and NO2 play a key role in atmospheric chemistry. Nitrous oxide, NO, and NO2 fluxes from fertilized soils were measured six times per day by an automated flux monitoring system for one year, beginning on 21 May 1998. Pac choi (Brassica spp.) was cultivated for two months, and the plots were left fallow the remainder of the year. Two types of manure, poultry manure (PM) and swine manure (SM), and a chemical fertilizer, urea, were applied to the soil. The total amount of nitrogen applied in each case was 15 g N m(-2). The total fluxes from PM, SM, and urea for the year were 184, 61.3, and 44.8 mg N m(-2) for N2O, respectively; 9.95, 16.6, and 148 mg N m(-2) for NO, respectively; and -6.21, -7.23, and -7.84 mg N m(-2) for NO2, respectively. A negative correlation was found between the NO flux and the NO concentration of the chamber air just after the chamber was closed, when a flux from the atmosphere to soil was observed for 10 months. The mean gross NO production, the NO uptake rate constant, and the apparent compensation point for this period were 0.79 to 0.95 microg N m(-2) h(-1), 120 to 128 L m(-2) h(-1), and 5.65 to 7.35 ppbv, respectively.     

特高含硫油气田废水中阴离子（F－、Cl－、Br－、SO）的离子色谱测定

论述了用国产的低压离子色谱仪、电导检测器作为测定特高含硫油气田废水中Ｆ－、Ｃｌ－、Ｂｒ－、ＳＯ离子的可行性，并讨论了分析条件、最低检出限、精密度、准确度以及干扰等，及对国家标样及实际样品进行了测定。结果表明该法简单、快速、灵敏、准确，是目前较为理想的测定特高含硫油气田废水中无机阴离子的方法。     

Denitrification in suburban lawn soils

There is great uncertainty about the fate of nitrogen (N) added to urban and suburban lawns. We used direct flux and in situ chamber methods to measure N and NO fluxes from lawns instrumented with soil O sensors. We hypothesized that soil O, moisture, and available NO were the most important controls on denitrification and that N and NO fluxes would be high following fertilizer addition and precipitation events. While our results support these hypotheses, the thresholds of soil O, moisture, and NO availability required to see significant N fluxes were greater than expected. Denitrification rates were high in saturated, fertilized soils, but low under all other conditions. Annual denitrification was calculated to be 14.0 ± 3.6 kg N ha yr, with 5% of the growing season accounting for >80% of the annual activity. Denitrification is thus an important means of removing reactive N in residential landscapes, but varies markedly in space, time, and with factors that affect soil saturation (texture, structure, compaction) and NO availability (fertilization). Rates of in situ NO flux were low; however, when recently fertilized soils saturated with water were incubated in the laboratory, we saw extraordinarily high rates of NO production for the first few hours of incubation, followed by rapid NO consumption later in the experiment. These findings indicate a lag time between accelerated NO production and counterbalancing increases in NO consumption; thus, we cannot yet conclude that lawns are an insignificant source of NO in our study area.     

Methane Emissions and Production Potentials of Forest Swamp Wetlands in the Eastern Great Xing’an Mountains, Northeast China

Measurements of methane flux at a few inundated sites in China have been extrapolated to obtain estimates on a national scale. To enable those national estimates to be refined and to compare flux from geographically separated sites comprising the same wetland types, we used a closed chamber method to measure methane flux in uninundated Betula platyphylla—and Larix gmelinii—dominated peatlands in the Northeast China. Our measurements were taken from both vegetated and bare soil surfaces, and we compared flux with environmental measures including vegetation biomass, soil temperature and soil characteristics. We found that methane flux was low, and that there were no significant differences between wetland types, indicating that environmental influences were dominant. We found that flux was positively correlated to temperature in the surface layers of the soil, the above-ground biomass of the shrub and herb layers, total soil carbon and total soil nitrogen; and we suggest that emissions may be due to anaerobic microcosms in the surface layers. The methane production potentials of the soils were low and similar between both sites but inconsistent with the differences between fluxes, and inconsistent with production potentials and fluxes reported from the same wetland types elsewhere, indicating that there were subtle environmental differences between wetlands classed as being of the same type. Differences between fluxes in vegetated chambers with bare soil chambers were insignificant, indicating that no methane emission through aerenchyma occurred at our sites. We concluded that wetland type was not an accurate predictor of methane flux.     

Aluminum output fluxes from forest ecosystems in Europe: a regional assessment

Data from 89 forested catchments and plots across Europe were used to define empirical relationships between aluminum leaching and input fluxes of major ions, output fluxes of major ions, ecosystem parameters such as soil pH, and combinations of these. Forests that release dissolved Al to seepage or surface waters are located primarily in areas receiving the highest loading of acid rain, and the output flux of Al shows the highest correlations to the throughfall flux of inorganic nitrogen, the output fluxes of NO3-, H+, and SO4(2-), and the mineral soil pH. If the speciation of Al is taken to be Al3+ (an overestimate), Al is released in a nearly 1:1 molar charge ratio with the sum of NO3- and SO4(2-) in runoff or seepage water over a wide range of basepoor bedrock types and acid deposition across Europe. The empirical data point to a threshold range of N deposition of 80 to 150 mmolc N m(-2) yr(-1) and a (less clearly defined) range of S deposition of 100 to 200 mmolc SO4(-2) m(-2) yr(-1) above which Al released from forests exceeds 100 mmolc Al m(-2) yr(-1). Within this threshold range, the sites that release little or no dissolved Al are those that continue to assimilate input N and/or have high soil pH (>4.5).     

UPLC-DAD-FLD测定土壤中多环芳烃

本文建立了以加速溶剂萃取（ASE）和固相萃取为提取和净化手段,采用超速液相色谱-二极管阵列-荧光检测器（UPLC-DAD-FLD）串联捡测土壤中16种多环芳烃的方法。通过色谱柱的比较,选择更小粒径和内径的分析柱（Supelco SILTMLC．PAH,100×3．0mm,3μm）,缩短了分析时间,也节省了溶剂（乙腈）,满足大量样品的快速灵敏分析的需要。在保留时间定性的基础上,利用PDA获取的紫外扫描光谱图与目标化合物的特征吸收标准谱图比较,提高了定性分析的准确性。在优化的实验条件下,该方法显示出良好的线性关系（r〉0．999）和精密度（RSD〈10％）,16种多环芳烃的检出限在0．005—1．33μg／kg之间,并成功应用于样品分析,样品加标回收率为71．4％～120％。实验中为了确保整个分析过程的可靠性,替代物的加标回收率控制在50％-150％之间;土壤标准参考物的测定结果都在预测值范围内,验证了该方法的准确性。     

A dynamic two-dimensional system for measuring volatile organic compound volatilization and movement in soils

There is an important need to develop instrumentation that allows better understanding of atmospheric emission of toxic volatile compounds associated with soil management. For this purpose, chemical movement and distribution in the soil profile should be simultaneously monitored with its volatilization. A two-dimensional rectangular soil column was constructed and a dynamic sequential volatilization flux chamber was attached to the top of the column. The flux chamber was connected through a manifold valve to a gas chromatograph (GC) for real-time concentration measurement. Gas distribution in the soil profile was sampled with gas-tight syringes at selected times and analyzed with a GC. A pressure transducer was connected to a scanivalve to automatically measure the pressure distribution in the gas phase of the soil profile. The system application was demonstrated by packing the column with a sandy loam in a symmetrical bed-furrow system. A 5-h furrow irrigation was started 24 h after the injection of a soil fumigant, propargyl bromide (3-bromo-1-propyne; 3BP). The experience showed the importance of measuring lateral volatilization variability, pressure distribution in the gas phase, chemical distribution between the different phases (liquid, gas, and sorbed), and the effect of irrigation on the volatilization. Gas movement, volatilization, water infiltration, and distribution of degradation product (Br-) were symmetric around the bed within 10%. The system saves labor cost and time. This versatile system can be modified and used to compare management practices, estimate concentration-time indexes for pest control, study chemical movement, degradation, and emissions, and test mathematical models.     

Tool for assessment of process importance at the groundwater/surface water interface

The groundwater/surface water interface (GWSWI) represents an important transition zone between groundwater and surface water environments that potentially changes the nature and flux of contaminants exchanged between the two systems. Identifying dominant and rate-limiting contaminant transformation processes is critically important for estimating contaminant fluxes and compositional changes across the GWSWI. A new, user-friendly, spreadsheet- and Visual Basic-based analytical screening tool that assists in evaluating the dominance of controlling kinetic processes across the GWSWI is presented. Based on contaminant properties, first-order processes that may play a significant role in solute transport/transformation are evaluated in terms of a ratio of process importance (P_i) that relates the process rate to the rate of fluid transfer. Besides possessing several useful compilations of contaminant and process data, the screening tool also includes 1-D analytical models that assist users in evaluating contaminant transport across the GWSWI. The tool currently applies to 29 organics and 10 inorganics of interest within the context of the GWSWI. Application of the new screening tool is demonstrated through an evaluation of natural attenuation at a site with trichloroethylene and 1,1,2,2-tetrachloroethane contaminated groundwater discharging into wetlands.     

QUALITY ASSURANCE TECHNIQUES FOR ELECTRONIC DATA ACQUISITION1

ABSTRACT: Electronic instruments are increasingly being used to gather water quality data. Quality assurance protocols are needed which provide adequate documentation of the procedures followed in calibration, collection, and validation of electronically acquired data. The level of precision of many data loggers exceeds the technology which is commonly used to make field measurements. Overcoming this problem involves using laboratory quality equipment in the field or enhanced quality control at the time of instrument servicing. Time control procedures for data loggers are needed to allow direct comparisons of data between instruments. Electronic instruments provide a mechanism to study transient events in great detail, but, without time controls, multiple loggers produce data which contain artifacts due to timing errors. Individual sensors deployed with data loggers are subject to different degrees of drift over time. Certain measurements can be measured with defined precision and accuracy for long periods of time, while other sensors are subject to loss of both precision and accuracy with increasing time of use. Adequate quality assurance requires the levels of precision and accuracy be documented, particularly those which vary with increasing time deployment.     

Laboratory-scale measurement of trace gas fluxes from landfarm soils

Trace gas emissions from refinery and bioremediation landfarms were investigated in a mesocosm-scale simulator facility. Five simulators were constructed and integrated with a data acquisition system and trace gas analyzers, allowing automated real-time sampling and calculation of total hydrocarbon (THC), CO2, and water vapor fluxes. Experiments evaluating the influence of simulated cultivation and rainfall on trace gas fluxes from the soil surfaces were conducted. Results were compared with published field results. Results showed that cultivating dry or moderately wet soil resulted in brief enhancements of THC fluxes, up to a factor of 10, followed by a sharp decline. Cultivating dry soil did not enhance respiration. Cultivating wet soil did result in sustained elevated levels of respiration. Total hydrocarbon emissions were also briefly enhanced in wet soils, but to a lesser magnitude than in dry soil. Hydrocarbon fluxes from refinery landfarm soil were very low for the duration of the experiments. This lead to the conclusion that elevated THC fluxes would only be expected during waste application. An evaluation of the influence of simultaneous water vapor fluxes on other trace gas fluxes highlighted the importance in lab-scale experiments of correcting trace gas fluxes from soils. The results from this research can be used to guide management practices at landfarms and to provide data to aid in assessing the effect of landfarms.     

Alcohol, volatile fatty acid, phenol, and methane emissions from dairy cows and fresh manure

There are approximately 2.5 million dairy cows in California. Emission inventories list dairy cows and their manure as the major source of regional air pollutants, but data on their actual emissions remain sparse, particularly for smog-forming volatile organic compounds (VOCs) and greenhouse gases (GHGs). We report measurements of alcohols, volatile fatty acids, phenols, and methane (CH4) emitted from nonlactating (dry) and lactating dairy cows and their manure under controlled conditions. The experiment was conducted in an environmental chamber that simulates commercial concrete-floored freestall cow housing conditions. The fluxes of methanol, ethanol, and CH4 were measured from cows and/or their fresh manure. The average estimated methanol and ethanol emissions were 0.33 and 0.51 g cow(-1) h(-1) from dry cows and manure and 0.7 and 1.27 g cow(-1) h(-1) from lactating cows and manure, respectively. Both alcohols increased over time, coinciding with increasing accumulation of manure on the chamber floor. Volatile fatty acids and phenols were emitted at concentrations close to their detection limit. Average estimated CH4 emissions were predominantly associated with enteric fermentation from cows rather than manure and were 12.35 and 18.23 g cow(-1) h(-1) for dry and lactating cows, respectively. Lactating cows produced considerably more gaseous VOCs and GHGs emissions than dry cows (P < 0.001). Dairy cows and fresh manure have the potential to emit considerable amounts of alcohols and CH4 and research is needed to determine effective mitigation.     

Laboratory-scale investigation of UV treatment of ammonia for livestock and poultry barn exhaust applications

The feasibility of using deep ultraviolet (UV) treatment for abatement of ammonia (NH(3)) in livestock and poultry barn exhaust air was examined in a series of laboratory-scale experiments. These experiments simulated moving exhaust air through an irradiation chamber with variables of UV wavelength and dose, NH(3) concentrations, humidity, and presence of hydrogen sulfide (H(2)S). Ammonia, initially at relevant barn exhaust concentrations in air, was substantially or completely reduced by irradiation with 185 nm light. Reactions were monitored using chemiluminescence detection, gas chromatography with mass spectrometry detection, and Fourier transform infrared spectrometry, of which the latter was found to be the most informative and flexible. Detected nitrogen-containing products included N(2)O, NH(4)NO(3), and HNO(3). It was presumed that atomic oxygen is the primary photochemical product that begins the oxidative cascade. The data show that removal of NH(3) is plausible, but they highlight concerns over pollution swapping due to formation of ozone and N(2)O.     

Measuring flux of soil fumigants using the aerodynamic and dynamic flux chamber methods

Methods for measuring and estimating flux density of soil fumigants under field conditions are important for the purpose of providing inputs to air dispersion models and for comparing the effects of management practices on emission reduction. The objective of this study was to measure the flux of 1,3-dichloropropene (1,3-D) and chloropicrin at a site in Georgia (GA) using the aerodynamic method and the dynamic flux chamber (FC) method. A secondary objective was to compare the effects of high density polyethylene (HDPE), and virtually impermeable film (VIF) tarps on fumigant flux at a site in Florida (FL). Chloropicrin and 1,3-D were applied by surface drip application of In-Line soil fumigant on vegetable beds covered by low density polyethylene (LDPE), HDPE, or VIF. The surface drip fumigation using In-Line and LDPE tarp employed in this study resulted in volatilization of 26.5% of applied 1,3-D and 11.2% of the applied chloropicrin at the GA site, as determined using the aerodynamic method. Estimates of mass loss obtained from dynamic FCs were 23.6% for 1,3-D and 18.0% for chloropicrin at the GA site. Flux chamber trials at the FL site indicate significant additional reduction in flux density, and cumulative mass loss when VIF tarp is used. This study supports the use of dynamic FCs as a valuable tool for estimating gas flux density from agricultural soils, and evaluating best management practices for reducing fumigant emissions to the atmosphere.