Characterizing ammonia emissions from swine farms in eastern North Carolina: part 1--conventional lagoon and spray technology for waste treatment

Ammonia (NH3) fluxes from waste treatment lagoons and barns at two conventional swine farms in eastern North Carolina were measured. The waste treatment lagoon data were analyzed to elucidate the temporal (seasonal and diurnal) variability and to derive regression relationships between NH3 flux and lagoon temperature, pH and ammonium content of the lagoon, and the most relevant meteorological parameters. NH3 fluxes were measured at various sampling locations on the lagoons by a flowthrough dynamic chamber system interfaced to an environmentally controlled mobile laboratory. Two sets of open-path Fourier transform infrared (FTIR) spectrometers were also used to measure NH3 concentrations for estimating NH3 emissions from the animal housing units (barns) at the lagoon and spray technology (LST) sites. Two different types of ventilation systems were used at the two farms. Moore farm used fan ventilation, and Stokes farm used natural ventilation. The early fall and winter season intensive measurement campaigns were conducted during September 9 to October 11, 2002 (lagoon temperature ranged from 21.2 to 33.6 degrees C) and January 6 to February 2, 2003 (lagoon temperature ranged from 1.7 to 12 degrees C), respectively. Significant differences in seasonal NH3 fluxes from the waste treatment lagoons were found at both farms. Typical diurnal variation of NH3 flux with its maximum value in the afternoon was observed during both experimental periods. Exponentially increasing flux with increasing surface lagoon temperature was observed, and a linear regression relationship between logarithm of NH3 flux and lagoon surface temperature (T1) was obtained. Correlations between lagoon NH3 flux and chemical parameters, such as pH, total Kjeldahl nitrogen (TKN), and total ammoniacal nitrogen (TAN) were found to be statistically insignificant or weak. In addition to lagoon surface temperature, the difference (D) between air temperature and the lagoon surface temperature was also found to influence the NH3 flux, especially when D > 0 (i.e., air hotter than lagoon). This hot-air effect is included in the statistical-observational model obtained in this study, which was used further in the companion study (Part II), to compare the emissions from potential environmental superior technologies to evaluate the effectiveness of each technology.     

Trends in snowpack chemistry and comparison to National Atmospheric Deposition Program results for the Rocky Mountains, US, 1993–2004

Seasonal snowpack chemistry data from the Rocky Mountain region of the US was examined to identify long-term trends in concentration and chemical deposition in snow and in snow-water equivalent. For the period 1993–2004, comparisons of trends were made between 54 Rocky Mountain Snowpack sites and 16 National Atmospheric Deposition Program wetfall sites located nearby in the region. The region was divided into three subregions: Northern, Central, and Southern. A non-parametric correlation method known as the Regional Kendall Test was used. This technique collectively computed the slope, direction, and probability of trend for several sites at once in each of the Northern, Central, and Southern Rockies subregions. Seasonal Kendall tests were used to evaluate trends at individual sites.Significant trends occurred during the period in wetfall and snowpack concentrations and deposition, and in precipitation. For the comparison, trends in concentrations of ammonium, nitrate, and sulfate for the two networks were in fair agreement. In several cases, increases in ammonium and nitrate concentrations, and decreases in sulfate concentrations for both wetfall and snowpack were consistent in the three subregions. However, deposition patterns between wetfall and snowpack more often were opposite, particularly for ammonium and nitrate. Decreases in ammonium and nitrate deposition in wetfall in the central and southern rockies subregions mostly were moderately significant (p<0.11) in constrast to highly significant increases in snowpack (p<0.02). These opposite trends likely are explained by different rates of declining precipitation during the recent drought (1999–2004) and increasing concentration. Furthermore, dry deposition was an important factor in total deposition of nitrogen in the region. Sulfate deposition decreased with moderate to high significance in all three subregions in both wetfall and snowpack. Precipitation trends consistently were downward and significant for wetfall, snowpack, and snow-telemetry data for the central and southern rockies subregions (p<0.03), while no trends were noted for the Northern Rockies subregion.     

Examining the joint toxicity of chlorpyrifos and atrazine in the aquatic species: Lepomis macrochirus, Pimephales promelas and Chironomus tentans

The joint toxicity of chlorpyrifos and atrazine was compared to that of chlorpyrifos alone to discern any greater than additive response using both acute toxicity testing and whole-body residue analysis. In addition, acetylcholinesterase (AChE) inhibition and biotransformation were investigated to evaluate the toxic mode of action of chlorpyrifos in the presence of atrazine. The joint toxicity of atrazine and chlorpyrifos exhibited no significant difference in Lepomis macrochirus compared to chlorpyrifos alone; while studies performed with Pimephales promelas and Chironomus tentans, did show significant differences. AChE activity and biotransformation showed no significant differences between the joint toxicity of atrazine and chlorpyrifos and that of chlorpyrifos alone. From the data collected, the combination of atrazine and chlorpyrifos pose little additional risk than that of chlorpyrifos alone to the tested fish species.     

Long term changes in atmospheric N and S throughfall deposition and effects on soil solution chemistry in a Scots pine forest in the Netherlands

In a Scots pine forest the throughfall deposition and the chemical composition of the soil solution was monitored since 1984. (Inter)national legislation measures led to a reduction of the deposition of nitrogen and sulphur. The deposition of sulphur has decreased by approximately 65%. The total mineral-nitrogen deposition has decreased by ca. 25%, which is mainly due to a reduction in ammonium-N deposition (−40%), since nitrate-N deposition has increased (+50%). The nitrogen concentration in the upper mineral soil solution at 10 cm depth has decreased, leading to an improved nutritional balance, which may result in improved tree vitality. In the drainage water at 90 cm depth the fluxes of NO₃⁻ and SO₄²⁻ have decreased, resulting in a reduced leeching of accompanying base cations, thus preserving nutrients in the ecosystem. It may take still several years, however, before this will meet the prerequisite of a sustainable ecosystem.     

Improved computational model (AQUIFAS) for activated sludge, integrated fixed-film activated sludge, and moving-bed biofilm reactor systems, Part I: Semi-empirical model development

Research was undertaken to develop a model for activated sludge, integrated fixed-film activated sludge (IFAS), and moving-bed biofilm reactor (MBBR) systems. The model can operate with up to 12 cells (reactors) in series, with biofilm media incorporated to one or more cells, except the anaerobic cells. The process configuration can be any combination of anaerobic, anoxic, aerobic, post-anoxic with or without supplemental carbon, and reaeration; it can also include any combination of step feed and recycles, including recycles for mixed liquor, return activated sludge, nitrates, and membrane bioreactors. This paper presents the structure of the model. The model embeds a biofilm model into a multicell activated sludge model. The biofilm flux rates for organics, nutrients, and biomass can be computed by two methods--a semi-empirical model of the biofilm that is relatively simpler, or a diffusional model that is computationally intensive. The values of the kinetic parameters for the model were measured using pilot-scale activated sludge, IFAS, and MBBR systems. For the semiempirical version, a series of Monod equations were developed for chemical oxygen demand, ammonium-nitrogen, and oxidized-nitrogen fluxes to the biofilm. Within the equations, a second Monod expression is used to simulate the effect of changes in biofilm thickness and fraction nitrifiers in the biofilm. The biofilm flux model is then linked to the activated sludge model. The diffusional model and the verification of the models are presented in subsequent papers (Sen and Randall, 2008a, 2008b). The model can be used to quantify the amount of media and surface area required to achieve nitrification, identify the best locations for the media, and optimize the dissolved oxygen levels and nitrate recycle rates. Some of the advanced features include the ability to apply different media types and fill fractions in cells; quantify nitrification, denitrification, and biomass production in the biofilm and mixed liquor suspended solids; and perform dynamic simulations.     

Development of a regenerable system employing silica-titania composites for the recovery of mercury from end-box exhaust at a chlor-alkali facility

The release of mercury to the environment is of particular concern because of its volatility, persistence, and tendency to bioaccumulate. The recovery of mercury from end-box exhaust at chlor-alkali facilities is important to prevent release into the environment and reduce emissions as required by NESHAP (National Emission Standards for Hazardous Air Pollutants). A pilot-scale photocatalytic reactor packed with silica-titania composite (STC) pellets was tested at a chloralkali facility over a 3-month period. This pilot reactor treated up to 10 ft3/min (ACFM) of end-box exhaust and achieved 95% removal. The pilot reactor was able to maintain excellent removal efficiency even with large fluctuations in influent mercury concentration (400-1600 microg/ft3). The STC pellets were regenerated ex situ by regeneration with hydrochloric acid and performed similarly to virgin STC pellets when returned to service. On the basis of these promising results, two full-scale reactors with in situ regeneration capabilities were installed and operated. After optimization, these reactors performed similarly to the pilot reactor. A cost analysis was performed comparing the treatment costs (i.e., cost per pound of mercury removed) for sulfur-impregnated activated carbon and the STC system. The STC proved to be both technologically and economically feasible for this installation.     

Preliminary evidence of a decline in perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) concentrations in American Red Cross blood donors

The purpose of this pilot study was to determine whether perfluorooctanesulfonate (PFOS,C(8)F(17)SO(3)(-)) and perfluorooctanoate (PFOA,C(7)F(15)CO(2)(-)) concentrations in American Red Cross blood donors from Minneapolis-St. Paul, Minnesota have declined after the 2000-2002 phase-out of perfluorooctanesulfonyl-fluoride (POSF, C(8)F(17)SO(2)F)-based materials by the primary global manufacturer, 3M Company. Forty donor plasma samples, categorized by age and sex, were collected in 2005, and PFOS and PFOA concentrations were compared to 100 (non-paired) donor serum samples collected in 2000 from the same general population that were analyzed at the time using ion-pair extraction methods with tetrahydroperfluorooctanesulfonate as an internal standard. Eleven of the 100 samples originally collected were reanalyzed with present study methods that involved (13)C- labeled PFOA spiked into the donor samples, original samples, control human plasma, and the calibration curve prior to extraction, and was used as a surrogate to monitor extraction efficiency. Quantification was performed by high performance liquid chromatography tandem mass spectrometry methods. Among the 100 serum samples analyzed for PFOS, the geometric mean was 33.1 ng ml(-1) (95% CI 29.8-36.7) in 2000 compared to 15.1 ng ml(-1) (95% CI 13.3-17.1) in 2005 (p<0.0001) for the 40 donor plasma samples. The geometric mean concentration for PFOA was 4.5 ng ml(-1) (95% CI 4.1-5.0) in 2000 compared to 2.2 ng ml(-1) (95% CI 1.9-2.6) in 2005 (p<0.0001). The decrease was consistent across donors' age and sex. To confirm these preliminary findings, additional sub-sets of year 2000 samples will be analyzed, and a much larger biomonitoring study of other locations is planned.     

Spatial and temporal variations and possible sources of dichlorodiphenyltrichloroethane (DDT) and its metabolites in rivers in Tianjin, China

Water, suspended solid (SS) and sediment samples were collected from nine water courses in Tianjin, China and analyzed for dichlorodiphenyltrichloroethane (DDT) and its metabolites (DDXs, including o,p'-,p,p'-DDT, DDD and DDE). The average DDX concentrations in water, SS and sediment were 59+/-30 ng l(-1), 2690+/-1940 ng g(-1)dry wt. and 340+/-930 ng g(-1)dry wt., respectively. Due to the termination of the extensive agricultural application and industrial manufacture, DDXs in river sediment decreased by one order of magnitude since 1970's and low DDT fractions in these sediments were observed. Still, DDXs in the sediments near the outlets of the major manufacturers remained relatively high attributed to the historic input. DDXs in sediment were also positively correlated with organic matter content. Spatial distributions of DDXs in SS and water was different from that in sediment. For SS, a negative correlation between DDX concentration and SS content indicated a dilution effect in many rivers. Dissolved organic carbon content was the major factor affecting DDX concentrations in water phase. Wastewater discharged from dicofol manufacturers and likely illegal agricultural application were the primary reasons causing high DDT (DDE+DDD) ratios in SS and water.     

Transport of simazine in unsaturated sandy soil and predictions of its leaching under hypothetical field conditions

The potential contamination of groundwater by herbicides is often controlled by processes in the vadose zone, through which herbicides travel before entering groundwater. In the vadose zone, both physical and chemical processes affect the fate and transport of herbicides, therefore it is important to represent these processes by mathematical models to predict contaminant movement. To simulate the movement of simazine, a herbicide commonly used in Chilean vineyards, batch and miscible displacement column experiments were performed on a disturbed sandy soil to quantify the primary parameters and processes of simazine transport. Chloride (Cl(-)) was used as a non-reactive tracer, and simazine as the reactive tracer. The Hydrus-1D model was used to estimate the parameters by inversion from the breakthrough curves of the columns and to evaluate the potential groundwater contamination in a sandy soil from the Casablanca Valley, Chile. The two-site, chemical non-equilibrium model was observed to best represent the experimental results of the miscible displacement experiments in laboratory soil columns. Predictions of transport under hypothetical field conditions using the same soil from the column experiments were made for 40 years by applying herbicide during the first 20 years, and then halting the application and considering different rates of groundwater recharge. For recharge rates smaller than 84 mm year(-1), the predicted concentration of simazine at a depth of 1 m is below the U.S. EPA's maximum contaminant levels (4 microg L(-1)). After eight years of application at a groundwater recharge rate of 180 mm year(-1) (approximately 50% of the annual rainfall), simazine was found to reach the groundwater (located at 1 m depth) at a higher concentration (more than 40 microg L(-1)) than the existing guidelines in the USA and Europe.     

Laboratory and field evaluation of crystallized DOW 704 oil on the performance of the Well Impactor Ninety-Six fFine particulate matter fractionator

Subsequent to the 1997 promulgation of the Federal Reference Method (FRM) for monitoring fine particulate matter (PM2.5) in ambient air, U.S. Environmental Protection Agency (EPA) received reports that the DOW 704 diffusion oil used in the method's Well Impactor Ninety-Six (WINS) fractionator would occasionally crystallize during field use, particularly under wintertime conditions. Although the frequency of occurrence on a nationwide basis was low, uncertainties existed as to whether crystallization of the DOW 704 oil may adversely affect a sampling event's data quality. In response to these concerns, EPA and the State of Connecticut Department of Environmental Protection jointly conducted a series of specialized tests to determine whether crystallized oil adversely affected the performance of the WINS fractionator. In the laboratory, an experimental setup used dry ice to artificially induce crystallization of the diffusion oil under controlled conditions. Using primary polystyrene latex calibration aerosols, standard size-selective performance tests of the WINS fractionator showed that neither the position nor the shape of the WINS particle size fractionation curve was substantially influenced by the crystallization of the DOW 704 oil. No large particle bounce from the crystallized impaction surface was observed. During wintertime field tests, crystallization of the DOW 704 oil did not adversely affect measured PM2.5 concentrations. Regression of measurements with crystallized DOW 704 versus liquid dioctyl sebacate (DOS) oil produced slope, intercept, and R2 values of 0.98, 0.1, and 0.997 microg/m3, respectively. Additional field tests validated the use of DOS as an effective impaction substrate. As a result of these laboratory and field tests, DOS oil has been approved by EPA as a substitute for DOW 704 oil. Since the field deployment of DOS oil in 2001, users of this alternative oil have not reported any operational problems associated with its use in the PM2.5 FRM. Limited field evaluation of the BGI very sharp cut cyclone indicates that it provides a viable alternative to the WINS fractionator.