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.     

Concrete with carpet recyclates: suitability assessment by surface energy evaluation

Worn out textile floor coverings are burdensome wastes that are degraded in landfill sites after a very long period of time. One of the ways to manage this kind of waste may be the use of carpet recyclate (CR) as an additive for concrete reinforcement. Therefore, an attempt was made to predict the effects of recyclate additives on the durability a concrete-carpet mixture by employing the method of assessing surface properties of components in the concrete-carpet recyclates composite. Testing was performed on carpet wastes, containing polyamide (PA) and polypropylene (PP) piles and butadiene-styrene resin with chalk filler (BSC) as back coating, to assess the suitability of CR additive for concrete reinforcement by surface energy evaluation. Based on the measurements of contact angles, the free surface energy of recyclate components was determined. The reversible work of adhesion at the interface between these components in dry and wet states was also calculated. The results show that CR with both PA and PP fibers form a strong and water-resistant bond with concrete.     

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.     

Simultaneous chemical and sensory characterization of volatile organic compounds and semi-volatile organic compounds emitted from swine manure using solid phase microextraction and multidimensional gas chromatography-mass spectrometry-olfactometry

Swine manure is associated with emissions of odor, volatile organic compounds (VOCs) and other gases that can affect air quality on local and regional scales. In this research, a solid phase microextraction (SPME) and novel multidimensional gas chromatography-mass spectrometry-olfactometry (MDGC-MS-O) system were used to simultaneously identify VOCs and related odors emitted from swine manure. Gas samples were extracted from manure headspace using Carboxen/polydimethylsiloxane (PDMS) 85-microm SPME fibers. The MDGC-MS-O system was equipped with two columns in series with a system of valves allowing transfer of samples between columns (heartcutting). The heartcuts were used to maximize the isolation, separation, and identification of compounds. The odor impact of separated compounds was evaluated by a trained panelist for character and intensity. A total of 295 compounds with molecular weights ranging from 34 to 260 were identified. Seventy one compounds had a distinct odor. Nearly 68% of the compounds for which reaction rates with OH* radicals are known had an estimated atmospheric lifetime <24 h.     

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.     

The present condition of the Vistula river catchment area and its impact on the Baltic Sea coastal zone

This review paper describes the state of the Vistula basin and the Baltic Sea area. The article is divided into two parts concerning the river and the Baltic coastal zone, respectively. Each part describes the geography and the environmental state of the region and gives an overview of the socio-economic conditions. The environmental state of the study regions is described in terms of annual monitoring data for the main physico-chemical and biological parameters. The data cover the last decade. The socio-economic overview includes parameters such as e.g. population density, industrialization, agricultureand land use.SI: Pirrone     

Repeatability study of replicate crash tests: A signal analysis approach

Objective: To provide an objective basis on which to evaluate the repeatability of vehicle crash test methods, a recently developed signal analysis method was used to evaluate correlation of sensor time history data between replicate vehicle crash tests. The goal of this study was to evaluate the repeatability of rollover crash tests performed with the Dynamic Rollover Test System (DRoTS) relative to other vehicle crash test methods.

Methods: Test data from DRoTS tests, deceleration rollover sled (DRS) tests, frontal crash tests, frontal offset crash tests, small overlap crash tests, small overlap impact (SOI) crash tests, and oblique crash tests were obtained from the literature and publicly available databases (the NHTSA vehicle database and the Insurance Institute for Highway Safety TechData) to examine crash test repeatability.

Results: Signal analysis of the DRoTS tests showed that force and deformation time histories had good to excellent repeatability, whereas vehicle kinematics showed only fair repeatability due to the vehicle mounting method for one pair of tests and slightly dissimilar mass properties (2.2%) in a second pair of tests. Relative to the DRS, the DRoTS tests showed very similar or higher levels of repeatability in nearly all vehicle kinematic data signals with the exception of global X′ (road direction of travel) velocity and displacement due to the functionality of the DRoTS fixture. Based on the average overall scoring metric of the dominant acceleration, DRoTS was found to be as repeatable as all other crash tests analyzed. Vertical force measures showed good repeatability and were on par with frontal crash barrier forces. Dynamic deformation measures showed good to excellent repeatability as opposed to poor repeatability seen in SOI and oblique deformation measures.

Conclusions: Using the signal analysis method as outlined in this article, the DRoTS was shown to have the same or better repeatability of crash test methods used in government regulatory and consumer evaluation test protocols.     

Pollution, Habitat Destruction, and Biodiversity in Poland

In the past 50 years, Poland has experienced unprecedented deterioration of the environment and loss of biodiversity. Emissions of toxic gases, such as SO₂, have reached 3 to 4 million tons annually, widely affecting flora, fauna, and human health. Almost all surface waters are heavily polluted. More than 75% of the water in the Vistula, Poland's largest river, is unsuitable even for industrial use. Environmental pollution, habitat loss and fragmentation, and industrialization of agricultural lands and forests have contributed to the loss of biodiversity. As many as 2500 plant species may be endangered (≈25% of all species) and approximately 228 (≈2%) have been extirpated from Poland. The largest losses of flora and fauna have occurred in wetland ecosystems. Among vertebrate species, 15 (≈2%) have been lost and more than 210 (another 30%) are endangered. Given the current economic uncertainty, it is difficult to predict future trends in pollutant emissions and their effects on Poland's biological diversity.