Multiplicative sensitivity analysis and its role in development of simulation models

A procedure of extended sensitivity analysis for simulation models is developed which is applicable to the situation in which input uncertainties are specified in a multiplicative (rather than an additive) way. This type of specification usually occurs when error estimates are large relative to the parameter values. The input parameter errors are assumed to have log-normal distributions and the basis for this assumption is explained along with the advantages it provides. The new procedure, multiplicative sensitivity analysis, is developed for the purposes of internal model validation and identification of priorities for specific experimental and theoretical studies needed for a particular system being modelled. The applicability of the procedure in the very early stages of a research program is its main advantage and further expands the rôle of simulation models.     

Distribution of mercury in di erent environmental compartments in the aquatic ecosystem of the coastal zone of the Southern Baltic Sea

The aim of this study was to characterize mercury (Hg) contamination in the coastal waters of the Southern Baltic Sea, and to investigate transformations of Hg in the initial links of the marine food chain. Concentrations of Hg in water, particulate matter, plankton and macrophytes at various stations in the coastal zone (a bay with restricted water exchange, near an industrial city, river mouths, and the open sea) were measured in 2006–2008. Hg concentrations observed in the Southern Baltic varied greatly, showing the highest average values in all environmental compartments near the river mouths. In shallow, sheltered parts of the gulf, where water exchange is restricted, Hg concentrations in the water and in macrophytes were elevated relative to those in the coastal zone of the deeper part of the bay and in the open Baltic. Distance to the river mouth, terrestrial runo , and quantity and quality of organic matter were more important than seasonal variations in controlling Hg and HgSPM concentrations in water samples. Mercury concentrations in the surface microlayer at the air/sea interface were over 10 times higher than those in the bulk surface water. Concentrations of Hg in macrophytes in the winter were significantly higher than those in the warm seasons (spring, summer, autumn). This was probably the combined e ect of higher availability of Hg in porewaters and leaf growth inhibition.     

Mean annual (222)Rn concentration in homes located in different geological regions of Poland: first approach to whole country area

The paper presents the results of year-long measurements of radon (²²²Rn) concentration inside 129 buildings in Poland in relation to the geological conditions of their foundation. The authors took into account the division of the country into tectonic units, as well as the lithology of the rocks forming the bedrock of these buildings. As expected, the highest value of mean annual ²²²Rn concentration (845 Bq/m³) was recorded in a building situated in the area of the Sudetes, while the highest geometric mean (characteristic of the expected log-normal data distribution) was calculated based on measurements from buildings located within the East-European craton, in the area of Mazury-Podlasie monocline, where it reached 231 Bq/m³. Such results reflect geological conditions - the occurrence of crystalline rocks (especially U- and Ra-enriched granites and orthogneisses) on the surface in the Sudetes, and of young post-glacial sediments containing fragments of Scandinavian crystalline rocks, also enriched with U and Ra, in the area of Mazury-Podlasie monocline. However, the least expected result of the investigations was finding out that, contrary to the hitherto widespread belief, none of the major tectonic units of Poland can be excluded from the list of those containing buildings with mean annual ²²²Rn concentration exceeding 200 Bq/m³. The mean annual concentration of radon for all the buildings were much higher than the mean concentration value (49.1 Bq/m³) of indoor radon in Poland quoted so far. These results cast a completely new light on the necessity to perform measurements of radon concentration in residential buildings in Poland, no more with reference to small areas with outcrops of crystalline rocks (especially the Sudetes, being the Polish fragment of the European Variscan belt), but for all the major tectonic units within Poland.     

A comparative study of the performance of passive samplers

Atmospheric concentrations of benzene, toluene, ethylbenzene, and xylenes (o-xylene and m,p-xylene) were assessed in the Tricity area (Gdańsk-Sopot-Gdynia, Poland) with the use of two types of passive samplers: permeation (homemade passive samplers) and diffusive (Radiello and Orsa 5). Samples were collected during 2008 at selected sites in the Tricity area at monitoring stations belonging to the agency of Regional Air Quality Monitoring Foundation. The field study was conducted to compare the performance of these two different types of passive samplers. A statistical approach was formulated, and the experimental data were evaluated using the paired t test, Wilcoxon signed rank-sum test, and Friedman analysis of variance. All the statistical results confirm the hypothesis that the differences between the performances of the three sampling devices are highly significant. Despite the fact that data obtained with the homemade passive sampler indicated that the results were higher compared with those for the Radiello and Orsa 5 diffusive samplers, the authors note that all differences between the homemade permeation sampler and the Radiello and Orsa 5 diffusive samplers are positive.     

Quality Assured Measurements of Animal Building Emissions: Gas Concentrations

Abstract

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH₃), hydrogen sulfide (H₂S), carbon dioxide (CO₂), methane (CH₄), nonmethane hydrocarbons (NMHC), particulate matter <10 µm in diameter, and total suspended particulate from swine and poultry production buildings in the United States.

This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with ≥10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH₃, H₂S, CO₂, CH₄, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Evaluation of Sample Recovery of Malodorous Livestock Gases from Air Sampling Bags,Solid-Phase Microextraction Fibers,Tenax TA Sorbent Tubes,and Sampling Canisters

Abstract

Odorous gases associated with livestock operations are complex mixtures of hundreds if not thousands of compounds. Research is needed to know how best to sample and analyze these compounds. The main objective of this research was to compare recoveries of a standard gas mixture of 11 odorous compounds from the Carboxen/PDMS 75–μm solid–phase microextraction fibers, polyvinyl fluo–ride (PVF; Tedlar), fluorinated ethylene propylene copolymer (FEP; Teflon), foil, and polyethylene terephthalate (PET; Melinex) air sampling bags, sorbent 2,b–diphenylene–oxide polymer resin (Tenax TA) tubes, and standard 6–L Stabilizer sampling canisters after sample storage for 0.5, 24, and 120 (for sorbent tubes only) hrs at room temperature. The standard gas mixture consisted of 7 volatile fatty acids (VFAs) from acetic to hexanoic, and 4 semivolatile organic compounds including p–cresol, indole, 4–ethylphenol, and 2'–aminoacetophenone with concentrations ranging from 5.1 ppb for indole to 1270 ppb for acetic acid. On average, SPME had the highest mean recovery for all 11 gases of 106.2%, and 98.3% for 0.5– and 24–hr sample storage time, respectively. This was followed by the Tenax TA sorbent tubes (94.8% and 88.3%) for 24 and 120 hr, respectively; PET bags (71.7% and 47.2%), FEP bags (75.4% and 39.4%), commercial Tedlar bags (67.6% and 22.7%), in–house–made Tedlar bags (47.3% and 37.4%), foil bags (16.4% and 4.3%), and canisters (4.2% and 0.5%), for 0.5 and 24 hr, respectively. VFAs had higher recoveries than semivolatile organic compounds for all of the bags and canisters. New FEP bags and new foil bags had the lowest and the highest amounts of chemical impurities, respectively. New commercial Tedlar bags had measurable concentrations of N,N–dimethyl acetamide and phenol. Foil bags had measurable concentrations of acetic, propionic, butyric, valeric, and hexanoic acids.     

The impact of land use and season on the riverine transport of mercury into the marine coastal zone

In Mediterranean seas and coastal zones, rivers can be the main source of mercury (Hg). Catchment management therefore affects the load of Hg reaching the sea with surface runoff. The major freshwater inflows to the Baltic Sea consist of large rivers. However, their systems are complex and identification of factors affecting the outflow of Hg from its catchments is difficult. For this reason, a study into the impact of watershed land use and season on mercury biogeochemistry and transport in rivers was performed along two small rivers which may be considered typical of the southern Baltic region. Neither of these rivers are currently impacted by industrial effluents, thus allowing assessment of the influence of catchment terrain and season on Hg geochemistry. The study was performed between June 2008 and May 2009 at 13 sampling points situated at different terrain types within the catchments (forest, wetland, agriculture and urban). Hg analyses were conducted by CVAFS. Arable land erosion was found to be an important source of Hg to the aquatic system, similar to urban areas. Furthermore, inflows of untreated storm water discharge resulted in a fivefold increase of Hg concentration in the rivers. The highest Hg concentration in the urban runoff was observed with the greatest amount of precipitation during summer. Moderate rainfalls enhance the inflow of bioavailable dissolved mercury into water bodies. Despite the lack of industrial effluents entering the rivers directly, the sub-catchments with anthropogenic land use were important sources of Hg in the rivers. This was caused by elution of metal, deposited in soils over the past decades, into the rivers. The obtained results are especially important in the light of recent environmental conscience regulations, enforcing the decrease of pollution by Baltic countries.     

Do evergreen and deciduous trees have different effects on net N mineralization in soil?

Evergreen and deciduous plants are widely expected to have different impacts on soil nitrogen (N) availability because of differences in leaf litter chemistry and ensuing effects on net N mineralization (N(min)). We evaluated this hypothesis by compiling published data on net N(min) rates beneath co-occurring stands of evergreen and deciduous trees. The compiled data included 35 sets of co-occurring stands in temperate and boreal forests. Evergreen and deciduous stands did not have consistently divergent effects on net N(min) rates; net N(min) beneath deciduous trees was higher when comparing natural stands (19 contrasts), but equivalent to evergreens in plantations (16 contrasts). We also compared net N(min) rates beneath pairs of co-occurring genera. Most pairs of genera did not differ consistently, i.e., tree species from one genus had higher net N(min) at some sites and lower net N(min) at other sites. Moreover, several common deciduous genera (Acer, Betula, Populus) and deciduous Quercus spp. did not typically have higher net N(min) rates than common evergreen genera (Pinus, Picea). There are several reasons why tree effects on net N(min) are poorly predicted by leaf habit and phylogeny. For example, the amount of N mineralized from decomposing leaves might be less than the amount of N mineralized from organic matter pools that are less affected by leaf litter traits, such as dead roots and soil organic matter. Also, effects of plant traits and plant groups on net N(min) probably depend on site-specific factors such as stand age and soil type.     

Evaluation of sample recovery of malodorous livestock gases from air sampling bags, solid-phase microextraction fibers, Tenax TA sorbent tubes, and sampling canisters

Odorous gases associated with livestock operations are complex mixtures of hundreds if not thousands of compounds. Research is needed to know how best to sample and analyze these compounds. The main objective of this research was to compare recoveries of a standard gas mixture of 11 odorous compounds from the Carboxen/PDMS 75-microm solid-phase microextraction fibers, polyvinyl fluoride (PVF; Tedlar), fluorinated ethylene propylene copolymer (FEP; Teflon), foil, and polyethylene terephthalate (PET; Melinex) air sampling bags, sorbent 2,b-diphenylene-oxide polymer resin (Tenax TA) tubes, and standard 6-L Stabilizer sampling canisters after sample storage for 0.5, 24, and 120 (for sorbent tubes only) hrs at room temperature. The standard gas mixture consisted of 7 volatile fatty acids (VFAs) from acetic to hexanoic, and 4 semivolatile organic compounds including p-cresol, indole, 4-ethylphenol, and 2'-aminoacetophenone with concentrations ranging from 5.1 ppb for indole to 1270 ppb for acetic acid. On average, SPME had the highest mean recovery for all 11 gases of 106.2%, and 98.3% for 0.5- and 24-hr sample storage time, respectively. This was followed by the Tenax TA sorbent tubes (94.8% and 88.3%) for 24 and 120 hr, respectively; PET bags (71.7% and 47.2%), FEP bags (75.4% and 39.4%), commercial Tedlar bags (67.6% and 22.7%), in-house-made Tedlar bags (47.3% and 37.4%), foil bags (16.4% and 4.3%), and canisters (4.2% and 0.5%), for 0.5 and 24 hr, respectively. VFAs had higher recoveries than semivolatile organic compounds for all of the bags and canisters. New FEP bags and new foil bags had the lowest and the highest amounts of chemical impurities, respectively. New commercial Tedlar bags had measurable concentrations of N,N-dimethyl acetamide and phenol. Foil bags had measurable concentrations of acetic, propionic, butyric, valeric, and hexanoic acids.     

Survey of dioxin sources in the Baltic Region (extended summary)

The present paper summarises the results of the project: 'Survey of Anthropogenic Sources of Dioxins and Furans in the Baltic Region'. As a part of the project, inventories have been carried out in Estonia, Latvia, Lithuania and Poland by applying the toolkit for quantification of dioxin and furan releases developed by UNEP Chemicals. The main route of direct releases to the environment is emission to air. Total emission to air from Poland was estimated at 490 (88-1,300) g I-TEQ/year, whereas the emissions from Estonia, Latvia and Lithuania were estimated as being 14 (2.4-54), 23 (2.6-63) and 17 (2.6-38) g I-TEQ, respectively. In general, the uncertainty on the estimates is very high, and recommendations regarding further development of the inventories have been made, and measures for reducing the releases have been provided.