Atmospheric Polycyclic Aromatic Hydrocarbons at a Point Source of Emissions. Part A: Identification and Determination of Polycyclic Aromatic Compounds in Airborne Particulate Matter Near a Horizontal Stud Soderberg Plant

Abstract

This paper summarizes the sampling and analytical methods developed to identify and measure polycyclic aromatic hydrocarbons (PAH) and related aromatic compounds near a Horizontal Stud Soderberg plant at Jonquiere, Quebec, Canada. The primary source of PAH is the coal tar pitch used as a binder in Soderberg anodes. Twice a week at a number of sampling sites, airborne particulate matter was collected on glass-fiber filters using a Hi-Vol sampler for a twenty-four hour period. Organics on the filter were Soxhlet extracted with benzene.

Identification was done by gas chromatography-mass spectrometry (GC-MS). The vast majority of compounds present were PAH, but small amounts of alkyl PAH and polycyclic aromatic compounds with heteroatoms such as nitrogen, oxygen and sulfur were also identified. Based on the GC-MS identification, a group of 14 PAH was selected for monitoring. Frequent PAH determinations revealed that the ratio of Benzo(a- )Pyrene to total PAH on the Hi-Vol filters is relatively constant in ambient air from one sampling station to another.     

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.     

Subpopulation structure of caribou (Rangifer tarandus L.) in arctic and subarctic Canada

Effective management and conservation of species, subspecies, or ecotypes require an understanding of how populations are structured in space. We used satellite-tracking locations and hierarchical and fuzzy clustering to quantify subpopulations within the behaviorally different barren-ground caribou (Rangifer tarandus groenlandicus), Dolphin and Union island caribou (R. t. groenlandicus x pearyi), and boreal (R. t. caribou) caribou ecotypes in the Northwest Territories and Nunavut, Canada. Using a novel approach, we verified that the previously recognized Cape Bathurst, Bluenose-West, Bluenose-East, Bathurst, Beverly, Qamanirjuaq, and Lorillard barren-ground subpopulations were robust and that the Queen Maude Gulf and Wager Bay barren-ground subpopulations were organized as individuals. Dolphin and Union island and boreal caribou formed one and two distinct subpopulation, respectively, and were organized as individuals. Robust subpopulations were structured by strong annual spatial affiliation among females; subpopulations organized as individuals were structured by migratory connectivity, barriers to movement, and/or habitat discontinuity. One barren-ground subpopulation used two calving grounds, and one calving ground was used by two barren-ground subpopulations, indicating that these caribou cannot be reliably assigned to subpopulations solely by calving-ground use. They should be classified by annual spatial affiliation among females. Annual-range size and path lengths varied significantly among ecotypes, including mountain woodland caribou (R. t. caribou), and reflected behavioral differences. An east-west cline in annual-range sizes and path lengths among migratory barren-ground subpopulations likely reflected differences in subpopulation size and habitat conditions and further supported the subpopulation structure identified.     

Measurement of gas diffusion through soils: comparison of laboratory methods

Gas movement through soils is important for ecosystems and engineering in many ways such as for microbial and plant respiration, passive methane oxidation in landfill covers and oxidation of mine residues. Diffusion is one of the most important gas movement processes and the determination of the diffusion coefficient is a crucial step in any study. Five laboratory methods used for measuring the relative gas diffusion coefficient (D(s)/D(o)) were compared using a loamy sand, a porous media commonly found in agricultural fields and in several engineered structures, such as in landfill final covers. In the absence of macropores, all methods gave rather similar values of D(s)/D(o). Methods allowing the study of microscale variability indicated that the presence of macropores highly influenced gas movement, thus the value of D(s)/D(o), which, near a macropore may be one order of magnitude higher than in regions without macropores. Repacked columns do not allow the study of heterogeneity in D(s)/D(o). Natural spatial variability in D(s)/D(o) due to water distribution and preferential pathways can only be studied in large systems, but these systems are difficult to handle. Advantages and disadvantages of each method are discussed.     

Regulation of spirocyst discharge in the model sea anemone, Nematostella vectensis

Test probes were touched to tentacles to investigate whether discharge of spirocysts likely is regulated by hair bundle mechanoreceptors. Significantly more spirocysts discharge onto test probes in the presence of vibrations at 11–15 Hz as compared to 0 Hz. Adding N-acetylneuraminic acid, NANA, shifts maximal discharge of spirocysts upwards to 36–40 Hz, and possibly to 21–25 Hz. In contrast, NANA shifts maximal discharge of basitrichous isorhiza nematocysts downwards to 1–20 Hz. Thus, discharge of cnidae (‘stinging capsules’) is differentially regulated according to the type of cnida. Furthermore, it appears that chemodetection of N-acetylated sugars is not a prerequisite to capturing prey because, in seawater alone, maximal discharge of cnidae occurs at frequencies overlapping movements of calmly swimming prey. Nevertheless, chemodetection of N-acetylated sugars broadens the range of frequencies stimulating maximal discharge of cnidae and, therefore, likely enhances prey capture.     

Transfer of CO2, N2O and CH4 to butyl rubber (polyisobutylene) septa during storage

Greenhouse gases are more sampled than ever because of environmental interests. Gas samples are often inserted into vials with gas tight butyl rubber septa before concentration analysis. Little is known on the global transfer property of butyl rubber septa for CO2, N2O and CH4. Sorption kinetics were measured by injecting CO2, N2O or CH4 into glass vials with either one of four butyl rubber septa types and stored during 90 days. CO2 and N2O concentrations decreased during storage depending upon septa type and initial concentration, with the highest linear rate being 0.023 for CO2 and 0.0015 mg L(-3) day(-1) for N2O. When a low concentration was injected, CH4 concentration changes over time were small and did not differ between septa types. Sorption isotherms were measured using nine concentrations and stored during 45 days. CO2 sorption isotherms ranged from 0 to 3.7 x 10(-3) m(3) m(-2) and N2O from 0.3 to 1.4 x 10(-3) m(3) m(-2). Examples of errors associated with the use of these butyl rubber septa are given.     

Sorption kinetics of chlortetracyline and tylosin on sandy loam and heavy clay soils

Antibiotics may appear in the environment when manure, sewage sludge, and other organic amendments are added to soils. There is concern that the presence of antibiotics in soils may lead to the development of antibiotic-resistant bacteria which may spread to the rest of the environment. This paper aims at evaluating the sorption kinetics of two antibiotics frequently used in pig production. The results indicate that sorption of chlortetracycline (CTC) and tylosin (TYL) in sandy loam and clay occurs very fast. More than 95% of the CTC adsorption is completed within 10 min on both soils and of TYL within 3 h. These results suggest that 24-h soil and antibiotic solution mixtures is enough for sorption studies. Also, there is less likelihood that these antibiotics will leach through soil and appear in the ground water since their sorption on soils is very high unless they are carried by soil particles through preferential flow. There was also no effect of soil sterilization on sorption kinetics of these antibiotics thus suggesting that there is minimal probability of the antibiotics degrading by microorganisms during 24- to 48-h adsorption studies.