Multicomponent simulation of wastewater-derived nitrogen and carbon in shallow unconfined aquifers. I. Model formulation and performance

One of the most common methods to dispose of domestic wastewater involves the release of septic effluent from drains located in the unsaturated zone. Nitrogen from such systems is currently of concern because of nitrate contamination of drinking water supplies and eutrophication of coastal waters. The objectives of this study are to develop and assess the performance of a mechanistic flow and reactive transport model which couples the most relevant physical, geochemical and biochemical processes involved in wastewater plume evolution in sandy aquifers. The numerical model solves for variably saturated groundwater flow and reactive transport of multiple carbon- and nitrogen-containing species in a three-dimensional porous medium. The reactive transport equations are solved using the Strang splitting method which is shown to be accurate for Monod and first- and second-order kinetic reactions, and two to four times more efficient than sequential iterative splitting. The reaction system is formulated as a fully kinetic chemistry problem, which allows for the use of several special-purpose ordinary differential equation (ODE) solvers. For reaction systems containing both fast and slow kinetic reactions, such as the combined nitrogen-carbon system, it is found that a specialized stiff explicit solver fails to obtain a solution. An implicit solver is more robust and its computational performance is improved by scaling of the fastest reaction rates. The model is used to simulate wastewater migration in a 1-m-long unsaturated column and the results show significant oxidation of dissolved organic carbon (DOC), the generation of nitrate by nitrification, and a slight decrease in pH.     

Influence of seaward boundary condition on contaminant transport in unconfined coastal aquifers.

Contaminant transport in coastal aquifers is complicated partly due to the conditions at the seaward boundary including seawater intrusion and tidal variations of sea level. Their inclusion in modelling this system will be computationally expensive. Therefore, it will be instructive to investigate the consequence of simplifying the seaward boundary condition by neglecting the seawater density and tidal variations in numerical predictions of contaminant transport in this zone. This paper presents a comparison of numerical predictions for a simplified seaward boundary condition with experimental results for a corresponding realistic one including a saltwater interface and tidal variations. Different densities for contaminants are considered. The comparison suggests that the neglect of the seawater intrusion and tidal variations does not affect noticeably the overall migration rate of the plume before it reaches the saltwater interface. However, numerical prediction shows that a more dense contaminant travels further seaward and part of the solute mass exits under the sea if the seawater density is not included. This is not consistent with the experimental result, which shows that the contaminant travels upwards to the shoreline along the saltwater interface. Neglect of seawater density, therefore, will result in an underestimation of the exit rate of solute mass around the coastline and fictitious migration paths under the seabed. For a less dense contaminant, neglect of seawater density has little effect on numerical prediction of migration paths.     

Effects of air filtration on spring wheat grown in open-top field chambers at a rural site. II. Effects on mineral partitioning, sulphur and nitrogen metabolism and on grain quality

In 1988 the effect of ambient levels of air pollutants on the nutrients status and grain quality of spring wheat (Triticum aestivum cv. Pelican) was investigated by comparing plants grown in open-top chambers (OTC) ventilated with ambient air (NF treatments) and charcoal-filtered air (CF treatments) at a rural site (Tervuren, Belgium). Spring wheat cultivated in NF OTC showed only minor differences in the P, K, Ca, Mg, Mn and Na concentrations of the different plant parts at final harvest, as well as organic and inorganic S fractions, compared to those of the plants grown in CF air. The plants' total P content was reduced, as well as the P and K concentration of the flour. The total S concentration of the flour was increased by 4%. Effects on N concentrations and grain quality were much more pronounced. At final harvest the N concentrations of straw and flour of the NF air treated plants were much higher compared to CF air. However, the N content of the aerial biomass and the grain N yield were not significantly affected, implying a reduction of other structual compounds. Nitrogen harvest index (NHI) and the ratio of NHI over grain harvest index (GHI), indicated a significant reduction of N translocation from the above-ground biomass to the grain. Changes in the N status and partitioning of spring wheat had an effect on the baking quality of wheat flour. Several parameters that are commonly used as an indication of baking quality have been significantly increased in the NF treatment: total protein concentration, Zeleny value, dry and wet gluten concentration. A slightly increased Hagberg value indicated a reduced alpha-amylase activity. The possibility of foliar N uptake as an additional N source, especially after anthesis and implications of increased protein production instead of carbohydrate synthesis are discussed.     

Production of carbon dioxide in a fattening pig house under field conditions. II. Release from the manure

Carbon dioxide (CO₂) release from manure was investigated under field conditions in one of the compartments in a mechanically ventilated fattening pig house. The potential of CO₂ release was tested in the emptied compartment by imposing high ventilation rate and measuring CO₂ concentrations in the incoming and exhaust air. When the compartment was filled with pigs, a model of tranquil CO₂ exhalation rate (TCER) was used to estimate the part of CO₂ produced by animals, in addition to the measurement of CO₂ concentrations and ventilation rate. Useful data were extracted from 135 days of continuously measured field data obtained when the housing system was in steady-state. The CO₂ release per m² of pit surface was 18.4 and 25.8 g h⁻¹ m⁻² in the emptied pig compartment during the impulse and pulse ventilation rate tests, respectively. It ranged from 1.1 and 116.7 g h⁻¹ m⁻² and averaged 42.1 g h⁻¹ m⁻² during the 135-day continuous field measurement. In 128 of the 135 days when the compartment was filled with pigs, the mean CO₂ release from the manure reached an average of 37.5% of the TCER by pigs, instead of less than 5% believed by many researchers. The maximum CO₂ release rate in 2-h steady-state measurements was 94% of the TCER by pigs. This research demonstrated that, in the previous knowledge, there might be a serious underestimation of the CO₂ release from the manure in pig houses. The total pig weight, manure temperature and ventilation rate were found the most important variables related to the CO₂ release. A mathematical model was developed to estimate the CO₂ release as a function of these three variables with R²=0.525.     

Temporal variability of groundwater chemistry in shallow and deep aquifers of Araihazar, Bangladesh

Samples were collected every 2-4 weeks from a set of 37 monitoring wells over a period of 2-3 years in Araihazar, Bangladesh, to evaluate the temporal variability of groundwater composition for As and other constituents. The monitoring wells are grouped in 6 nests and span the 5-91 m depth range. Concentrations of As, Ca, Fe, K, Mg, Mn, Na, P, and S were measured by high-resolution ICPMS with a precision of 5% or better; concentrations of Cl were measured by ion chromatography. In shallow wells <30 m deep, As and P concentrations generally varied by <30%, whereas concentrations of the major ions (Na, K, Mg, Ca and Cl) and the redox-sensitive elements (Fe, Mn, and S) varied over time by up to +/-90%. In wells tapping the deeper aquifers >30 m often below clay layers concentrations of groundwater As were much lower and varied by <10%. The concentrations of major cations also varied by <10% in these deep aquifers. In contrast, the concentration of redox-sensitive constituents Fe, S, and Mn in deep aquifers varied by up to 97% over time. Thus, strong decoupling between variations in As and Fe concentrations is evident in groundwaters from shallow and deep aquifers. Comparison of the time series data with groundwater ages determined by (3)H/(3)He and (14)C dating shows that large seasonal or inter-annual variations in major cation and chloride concentrations are restricted to shallow aquifers and groundwater recharged <5 years ago. There is no corresponding change in As concentrations despite having significant variations of redox sensitive constituents in these very young waters. This is attributed to chemical buffering due to rapid equilibrium between solute and solid As. At two sites where the As content of groundwater in existing shallow wells averages 102 microg/L (range: <5 to 648 microg/L; n=118) and 272 microg/L (range: 10 to 485 microg/L; n=65), respectively, a systematic long-term decline in As concentrations lends support to the notion that flushing may slowly deplete an aquifer of As. Shallow aquifer water with >5 years (3)H/(3)He age show a constant As:P molar ratio of 9.6 over time, suggesting common mechanisms of mobilization.     

Ozone disintegration of excess biomass and application to nitrogen removal.

A pilot-scale facility integrated with an ozonation unit was built to investigate the feasibility of using ozone-disintegration byproducts of wasted biomass as a carbon source for denitrification. Ozonation of biomass resulted in mass reduction by mineralization as well as by ozone-disintegrated biosolids recycling. Approximately 50% of wasted solids were recovered as available organic matter (ozonolysate), which included nonsettleable microparticles and soluble fractions. Microparticles were observed in abundance at relatively low levels of ozone doses, while soluble fractions became dominant at higher levels of ozone doses in ozone-disintegrated organics. Batch denitrification experiments showed that the ozonolysate could be used as a carbon source with a maximum denitrification rate of 3.66 mg nitrogen (N)/g volatile suspended solids (VSS) x h. Ozonolysate was also proven to enhance total nitrogen removal efficiency in the pilot-scale treatment facility. An optimal chemical oxygen demand (COD)-to-nitrogen ratio for complete denitrification was estimated as 5.13 g COD/g N. The nitrogen-removal performance of the modified intermittently decanted extended aeration process dependent on an external carbon supply could be described as a function of solids retention time.     

一体化A/O工艺碳氮比对脱氮除碳的影响

依据好氧硝化和缺氧反硝化生物脱氮除碳工艺原理,设计了一体化生物膜法A/O反应器,并将其应用于生活污水处理,取得了理想的处理效果。实验结果表明,水力停留时间HRT＝12 h,COD进水浓度处于150～500 mg/L范围内,COD的去除率均在90%以上,且出水均在40 mg/L以下;当C/N比为8.5以下时,NH₃-N去除率高于90%,其出水浓度小于5 mg/L;当C/N比为7.5左右时,具有较高的总氮脱除效果,TN去除率可达到70%。     

Growth, respiration and nitrogen content in needles of Scots pine exposed to elevated ozone and carbon dioxide in the field

Single Scots pine (Pinus sylvestris L.) trees, aged 30 years, were grown in open-top chambers and exposed to two atmospheric concentrations of ozone (O3; ambient and elevation) and carbon dioxide (CO2) as single variables or in combination for 3 years (1994-1996). Needle growth, respiration and nitrogen content were measured simultaneously over the period of needle expansion. Compared to ambient treatment (33 nmol mol(-1) O3 and 350 micromol mol(-1) CO2) doubled ambient O3 (69 nmol mol(-1)) significantly reduced the specific growth rates (SGRs) of the needles in the early stage of needle expansion and needle nitrogen concentration (N1) in the late stage, but increased apparent respiration rates (ARRs) in the late stage. Doubled ambient CO2 (about 650 micromol mol(-1)) significantly increased maximum SGR but reduced ARR and N1 in the late stage of needle expansion. The changes in ARR induced by the different treatments may be associated with treatment-induced changes in needle growth, metabolic activities and turnover of nitrogenous compounds. When ARR was partitioned into its two functional components, growth and maintenance respiration, the results showed that neither doubled ambient O3 nor doubled ambient CO2 influenced the growth respiration coefficients (Rg). However, doubled ambient O3 significantly increased the maintenance respiration coefficients (Rm) regardless of the needle development stage, while doubled ambient CO2 significantly reduced Rm only in the late stage of needle expansion. The increase in Rm under doubled ambient O3 conditions appeared to be related to an increase in metabolic activities, whereas the decrease in Rm under doubled ambient CO2 conditions may be attributed to the reduced N1 and turnover rate of nitrogenous compounds per unit. The combination of elevated O3 and CO2 had very similar effects on growth, respiration and N1 to doubled ambient O3 alone, but the interactive mechanism of the two gases is still not clear.     

Electrokinetic ion transport through unsaturated soil: 2. Application to a heterogeneous field site

Results of a field demonstration of electrokinetic transport of acetate through an unsaturated heterogeneous soil are compared to numerical modeling predictions. The numerical model was based on the groundwater flow and transport codes MODFLOW and MT3D modified to account for electrically induced ion transport. The 6-month field demonstration was conducted in an unsaturated layered soil profile where the soil moisture content ranged from 4% to 28% (m3 m(-3)). Specially designed ceramic-cased electrodes maintained a steady-state moisture content and electric potential field between the electrodes during the field demonstration. Acetate, a byproduct of acetic acid neutralization of the cathode electrolysis reaction, was transported from the cathode to the anode by electromigration. Field demonstration results indicated preferential transport of acetate through soil layers exhibiting higher moisture content/electrical conductivity. These field transport results agree with theoretical predictions that electromigration velocity is proportional to a power function of the effective moisture content. A numerical model using a homogeneous moisture content/electrical conductivity domain did not adequately predict the acetate field results. Numerical model predictions using a three-layer electrical conductivity/moisture content profile agreed qualitatively with the observed acetate distribution. These results suggest that field heterogeneities must be incorporated into electrokinetic models to predict ion transport at the field-scale.     

Prediction of carbon monoxide acute air pollution episodes. Model formulation and first application in Lombardy

This paper describes a method to forecast the exceedance probability of a fixed threshold for a certain air pollutant concentration. This general approach has been applied in the case of carbon monoxide on 35 traffic monitoring stations in the Lombardy Region. The implemented model has been called FOREPOLL (Forecast Pollution).The model structure, consisting in three basic modules (the deterministic, the stochastic and the Bayesian one), has been thought to be adjustable to different stations of an air quality network and to various pollutants. Forepoll uses the last biennium data set of the station in exam (pollutants and micrometeorological parameters) as a moving learning time and also needs the forecasted synoptic weather type. In the first module the daily maxima of the hourly measured pollutant concentrations are checked in order to eliminate some known physical dependencies, such as the temperature dependence of the emissions. Then the data are divided into subgroups depending on the weather type and in each group fitted by a different Weibull distribution. To provide a first a priori exceedance probability, this distribution is daily rebuilt by taking into account the forecasted parameters. In the last module this probability is enhanced or reduced using simple, experience based, bayesian rules providing the a posteriori exceedance probability.Model validation trials have been carried out on a year of CO forecasted concentrations in different air quality stations; the first results are quite good particularly for the metropolitan areas, because the model seems to work better in case of stronger and more diffuse pollution.     

Application and field validation of a continuous nonmethane organic carbon analyzer.

Nonmethane organic carbon (NMOC) is a measure of total organic carbon except for that from CH4. We recently reported the development of online instrumentation for continuous NMOC monitoring. This instrument, referred to as C-NMOC, uses a microsorbent trap in combination with a gas-sampling valve as the sampling interface. A conventional oxidation/reduction NMOC detector is used for quantitation. In addition to being an online concentrator and an injector, the microtrap serves as a separator that isolates NMOC from H2O, CO, CO2, CH4, and other background gases. Therefore, the C-NMOC is able to handle high concentrations of background gases commonly found in stack emissions and has detection limits in the ppb levels. This paper reports the results of field validation and testing of a C-NMOC analyzer at a coatings facility in the eastern United States. The instrument was able to monitor the process transients in real time, based on which corrective actions could be taken. It demonstrated good accuracy, high precision, and long-term stability.     

反硝化碳源在人工湿地脱氮中的应用及其研究进展

碳源供给是制约人工湿地反硝化脱氮的重要因素,系统论述了反硝化碳源的类型及其在人工湿地反硝化过程中的作用,并对人工湿地中反硝化碳源的应用现状进行了讨论.反硝化菌与人工湿地脱氮有着密切关联,是人工湿地领域研究的焦点.此外,人工湿地中的环境条件、运行条件及湿地构建条件等都会对其反硝化效果产生重要影响,指出了通过改善上述条件提...     

Hydrogeological and biogeochemical constrains of arsenic mobilization in shallow aquifers from the Hetao basin, Inner Mongolia

Little is known about the importance of drainage/irrigation channels and biogeochemical processes in arsenic distribution of shallow groundwaters from the Hetao basin. This investigation shows that although As concentrations are primarily dependent on reducing conditions, evaporation increases As concentration in the centre of palaeo-lake sedimentation. Near drainage channels, groundwater As concentrations are the lowest in suboxic-weakly reducing conditions. Results demonstrate that both drainage and irrigation channels produce oxygen-rich water that recharges shallow groundwaters and therefore immobilize As. Groundwater As concentration increases with a progressive decrease in redox potential along the flow path in an alluvial fan. A negative correlation between SO₄²⁻ concentrations and δ³⁴S values indicates that bacterial reduction of SO₄²⁻ occurs in reducing aquifers. Due to high concentrations of Fe (>0.5 mg L⁻¹), reductive dissolution of Fe oxides is believed to cause As release from aquifer sediments. Target aquifers for safe drinking water resources are available in alluvial fans and near irrigation channels.     

Modeling transport and fate of nitrogen from urea applied to a near-trench paddy field

A simple but comprehensive model is developed to quantify N losses from urea applied to a near-trench paddy field, considering all the N-transformations such as urea hydrolysis, volatilization, nitrification, denitrification, and all the important transportations like runoff, lateral seepage, vertical leaching and crop uptake. Seasonal average data of field observations for three crop seasons were used for model calibration and validation, which showed that ammonia volatilization accounted for 26.5-29.4% of the applied N and N uptake by crop occupied 38.2-44.8%, while N losses via surface runoff, vertical leaching and lateral seepage varied from 5.6-7.7%, 4.0-4.9% to 5.0-5.3% of the applied N, respectively. These observed results were well predicted by our model, indicating that the model performed effectively at quantifying N losses via individual processes in a wide range of urea application rates and benefit for developing water and fertilizer management strategies for near-trench paddy fields.     

Application of in situ biosparging to remediate a petroleum-hydrocarbon spill site: field and microbial evaluation

In this study, a full-scale biosparging investigation was conducted at a petroleum-hydrocarbon spill site. Field results reveal that natural attenuation was the main cause of the decrease in major contaminants [benzene, toluene, ethylbenzene, and xylenes (BTEX)] concentrations in groundwater before the operation of biosparging system. Evidence of the occurrence of natural attenuation within the BTEX plume includes: (1) decrease of DO, nitrate, sulfate, and redox potential, (2) production of dissolved ferrous iron, sulfide, methane, and CO(2), (3) decreased BTEX concentrations along the transport path, (4) increased microbial populations, and (5) limited spreading of the BTEX plume. Field results also reveal that the operation of biosparging caused the shifting of anaerobic conditions inside the plume to aerobic conditions. This variation can be confirmed by the following field observations inside the plume due to the biosparging process: (1) increase in DO, redox potential, nitrate, and sulfate, (2) decrease dissolved ferrous iron, sulfide, and methane, (3) increased total cultivable heterotrophs, and (4) decreased total cultivable anaerobes as well as methanogens. Results of polymerase chain reaction, denaturing gradient gel electrophoresis, and nucleotide sequence analysis reveal that three BTEX biodegraders (Candidauts magnetobacterium, Flavobacteriales bacterium, and Bacteroidetes bacterium) might exist at this site. Results show that more than 70% of BTEX has been removed through the biosparging system within a 10-month remedial period at an averaged groundwater temperature of 18 degrees C. This indicates that biosparging is a promising technology to remediate BTEX contaminated groundwater.     

Investigations of nitrogen fluxes and pools on a limestone site in the Alps

In the North Tyrolean Limestone Alps a site was investigated over a four-year period (1998–2001) in order to assess the nitrogen saturation status, the nitrogen budget (quantification of the net uptake of nitrogen by the canopy and of the nitrogen mineralization, nitrogen uptake from roots and N₂O emission rates, proof of the origin of nitrate in the soil water with stable isotope analyses), and the effects of the actual nitrogen input on ground water quality. The main goals were to quantify the nitrogen input rate, the nitrogen pools in above-ground and below-ground compartments, nitrogen turnover processes in the soil as well as the output into the groundwater and into the atmosphere. The findings are based on continuous and discontinuous field measurements as well as on model results.While nitrogen input exceeded the Critical Loads of the WHO (1995), nitrogen deficiency and nutrient imbalances were verified by needle analyses. The atmospheric input of inorganic nitrogen was higher than the nitrogen output in 50 cm soil depth. A tracer experiment with¹⁵N helped to prove that not more than half of the applied nitrate could be discharged. This allows the conclusion that nitrogen is stored in the system and that the site cannot yet be said to be saturated with nitrogen. The same result was also obtained by modelling. In addition, it was proved that the nitrogen discharge did not stem from deposition but from processes within the system.     

水泥预分解炉内流场及温度场的数值模拟

以某水泥厂分解炉为研究对象,采用CFD数值模拟方法,模拟了分解炉内气相流、气固两相流、煤粉燃烧和生料分解,分析现有分解炉内流场、颗粒相和温度场的分布情况。结果表明,该水泥厂分解炉只有一个三次风进口导致炉内流场分布不均匀,物料分散性不好,炉内温度分布不均匀,可采用错落式格局确定SNCR还原剂喷嘴位置,喷嘴位置应安装在20 m高度以上。基于模拟结果,提出分解炉改进方案,对称增加一个三次风进口。改进后炉内流场和温度场分布均匀,颗粒相的分散性得到改善。对结构对称式分解炉可采用同平面格局确定SNCR喷嘴位置。     

Riverine inputs of organic carbon and nitrogen to Norwegian coastal areas

The transport of organic and inorganic material in 10 Norwegian rivers has been monitored from 1990 to 1998. The suspended material in the rivers consisted of 40-80% organic materials. A major part of this was DOC with a C/ N mole ratio > 25. The C/N ratio of the organic material increases with increasing river flow when drained from forest-dominated catchments, in contrast to mountain dominated catchments where variation in runoff does not influence the C/N ratio. Laboratory experiments showed that more than 90% of the DOC remained in solution when salinity increased to 30. The flocculated and settled material contained less than 5% organic material with a C/N ratio of 6.7-12.4, comparable to C/N ratios in cultivated soils and coastal marine sediments. This confirms that only a minor amount of organic material carried to the sea by rivers settles in the coastal zone.     

Sulfur and carbon cycling in a flue gas desulfurization sludge disposal site

Products of a power plant flue gas desulfurization scrubber are discharged into a pond as sludge consisting of calcite (initial delta13C 3.2-3.8 per thousand), gypsum (initial delta34S 7.6-8.6 per thousand), and aqueous solution. Reducing conditions exist below a boundary that appears to move vertically as a function of changes in pond water level. Under reducing conditions, bacteria partially reduce aqueous sulfate to low-delta34S sulfide, consuming organic carbon and generating low-delta13C bicarbonate. Under oxidizing conditions, sulfide is converted to sulfate, leading to calcite dissolution, gypsum precipitation, and isotopic re-equilibration of remaining calcite with dissolved bicarbonate near the pond surface. The gypsum has delta34S near 6 per thousand, and calcite has delta13C as low as -1.7 per thousand; the changes from initial values correspond to predictions based on isotopic balance and reaction stoichiometry. The pond largely contains the products of bacterial reduction. After the pond is abandoned, these products may adversely affect attempts to revegetate the site. Future bacterial reduction may be best controlled by dewatering and limiting the supply of organic matter in percolating surface water.     

Degradation rates of CFC-11, CFC-12 and CFC-113 in anoxic shallow aquifers of Araihazar, Bangladesh

Chlorofluorocarbons CFC-11 (CCl(3)F), CFC-12 (CCl(2)F(2)), and CFC-113 (CCl(2)F-CClF(2)) are used in hydrology as transient tracers under the assumption of conservative behavior in the unsaturated and saturated soil zones. However, laboratory and field studies have shown that these compounds are not stable under anaerobic conditions. To determine the degradation rates of CFCs in a tropical environment, atmospheric air, unsaturated zone soil gas, and anoxic groundwater samples were collected in Araihazar upazila, Bangladesh. Observed CFC concentrations in both soil gas and groundwater were significantly below those expected from atmospheric levels. The CFC deficits in the unsaturated zone can be explained by gas exchange with groundwater undersaturated in CFCs. The CFC deficits observed in (3)H/(3)He dated groundwater were used to estimate degradation rates in the saturated zone. The results show that CFCs are degraded to the point where practically no (<5%) CFC-11, CFC-12, or CFC-113 remains in groundwater with (3)H/(3)He ages above 10 yr. In groundwater sampled at our site CFC-11 and CFC-12 appear to degrade at similar rates with estimated degradation rates ranging from approximately 0.25 yr(-1) to approximately 6 yr(-1). Degradation rates increased as a function of reducing conditions. This indicates that CFC dating of groundwater in regions of humid tropical climate has to be carried out with great caution.