Secondary Organic Aerosol Composition Studies Using Mass Spectrometry

Trace volatile organic compounds emitted by biogenic and anthropogenic sources into the atmosphere can undergo extensive photooxidation to form species with lower volatility. By equilibrium partitioning or reactive uptake, these compounds can nucleate into new aerosol particles or deposit onto already-existing particles to form secondary organic aerosol (SOA). SOA and other atmospheric particulate matter have measurable effects on global climate and public health, making understanding SOA formation a needed field of scientific inquiry. SOA formation can be done in a laboratory setting, using an environmental chamber; under these controlled conditions it is possible to generate SOA from a single parent compound and study the chemical composition of the gas and particle phases. By studying the SOA composition, it is possible to gain understanding of the chemical reactions that occur in the gas phase and particle phase, and identify potential heterogeneous processes that occur at the surface of SOA particles. In this thesis, mass spectrometric methods are used to identify qualitatively and qualitatively the chemical components of SOA derived from the photooxidation of important anthropogenic volatile organic compounds that are associated with gasoline and diesel fuels and industrial activity (C12 alkanes, toluene, and o-, m-, and p-cresols). The conditions under which SOA was generated in each system were varied to explore the effect of NO_x and inorganic seed composition on SOA chemical composition. The structure of the parent alkane was varied to investigate the effect on the functionalization and fragmentation of the resulting oxidation products. Relative humidity was varied in the alkane system as well to measure the effect of increased particle-phase water on condensed-phase reactions. In all systems, oligomeric species, resulting potentially from particle-phase and heterogeneous processes, were identified. Imines produced by reactions between (NH₄)₂SO₄ seed and carbonyl compounds were identified in all systems. Multigenerational photochemistry producing low- and extremely low-volatility organic compounds (LVOC and ELVOC) was reflected strongly in the particle-phase composition as well.

On methods of evaluation of bacterial production. [Translation from: Lietuvas TSR Mokslu Akademijos Darbai, C Serija 2(55) 3-9, 1971.]

By now a great deal of work is known concerning the methods of determining the production of bacteria or similar questions; among these the problems of a common terminology is discussed. The article discusses formulae of production of bacterial populations over time.

Growth and reproduction of Moina rectirostris (Leydig) and Ceriodaphnia quadrangula (O. F. Muller) with feeding on detritus. [Translation from: Sbornik po prudovomu rybovodstvu, 79-89. Moscow, VNIRO, 1969.]

The significance of detritus in the nutrition of aquatic animals, especially of the small representatives of the zooplankton, has been studied very slightly. Research so far has established that in M. rectirostris with feeding on protococcal and single-celled green algae and bacteria the beginning of formation of eggs takes place in 2 - 4 days. The young appear in 4 - 6 days. In this study M. rectirostris and C. quadrangula are fed on detritus of natural origin in laboratory conditions. In order to determine the assimilability and productive: effect of detritus, the author set up experiments, permitting to characterize the rate of growth, speed of maturing and fertility of M. rectirostris and C. quadrangula with feeding of them on detritus of different composition and age.

Comparison of permanent and temporary streams of calcareous Provence [Translation from: Annales de Limnologie 9(3) 273-292, 1973]

The rainfall regime and the karstic nature of the subsoil determines the alternation of a period of flow and a period of drought for a large number of Mediterranean streams. Amongst this type of stream it is possible to distinguish temporary streams, characterised by a period of flow for several months permitting the establishment of the principal groups of aquatic insects; and ephemeral streams whose very brief period of flow permits the establishment of a community reduced to a few species of Diptera. This paper aims to study the structure of the communities which colonise this particular type of stream and the ecology of the principal species which constitute these communities. Four French temporary streams were examined and temperature regimes, dissolved oxygen, calcium and magnesium measured. Samples of fauna were taken regularly and the biotic composition established. The analysis of similarities between the three permanent streams are discussed and compared with permanent streams.

Flood circulation in oligomictic lakes: an undervalued reason for restriction of zooplankton production [Translation from: Memorie dell'Istituto Italiano di Idrobiologia Dott.Marco de Marchi 22 9-52, 1967]

Dormancy has been observed in several species of Cyclops. Animals in dormancy are characterised by almost complete inactivity of the main appendages and sluggish intestinal peristalsis. In Cyclops vicinus dormancy can take place in copepod stages III (19%), IV (78%) and V (3%) but one and the same animal only in one developmental stage. The author gives his own results between frequency of dormancy and photoperiod (20 C, 1000 lux). He concludes that dormancy in C. vicinus can be influenced by day length and can be ended prematurely by short day length.

On new or insufficiently-known Chytridinae [Translation from: Archiv fur Protistenkunde 54 168-173 + pl.9, 1926]

This partial translation of a larger paper provides taxonomic descriptions of 5 fungal zoospores species: Olpidium vampyrellae, 0. pseudosporearum, 0. leptophrydis, Rhizophidium leptophrydis and Chytridium lateoperculatum.

Calcareous concretions in the Levriere (tributary of the Epte, secondary tributary of the Seine, Eure department) [Translation from: Bull.Ass.fr.Etud.Quaternaire 1973(2), 79-87, 1973]

From research carried, out on a section of the Levriere, concretions (granules, nodules, which were sometimes joined together) partly covering the river ”bottom” were observed. The authors propose to make besides a petrographic examination of the calcareous precipitations and to see if their origin is connected to a biological activity, or if it is purely a case of a physical-chemical precipitation. The hydrological background of the Levriere, a small river of the Normandy Vexin, is given and conditions of the formation of the concretions studied.

Rearing cyprinid fry in cages [conclusions only] [Translation from: Gospodarka rybna, Warszawa 27(8/9) 3-5, 1975]

This short translation presents the conclusions only of a study of the proposed method of rearing cyprinid fry in cages and how this method can increase the amount of material produced of the stocked fry.

I. Electron spin relaxation studies of manganese(II) complexes in acetonitrile. II. Nuclear spin relaxation studies of bromine in tetrabromomanganese(II) in acetonitrile

Magnetic resonance techniques have given us a powerful means for investigating dynamical processes in gases, liquids and solids. Dynamical effects manifest themselves in both resonance line shifts and linewidths, and, accordingly, require detailed analyses to extract desired information. The success of a magnetic resonance experiment depends critically on relaxation mechanisms to maintain thermal equilibrium between spin states. Consequently, there must be an interaction between the excited spin states and their immediate molecular environment which promote changes in spin orientation while excess magnetic energy is coupled into other degrees of freedom by non-radiative processes. This is well known as spin-lattice relaxation. Certain dynamical processes cause fluctuations in the spin state energy levels leading to spin-spin relaxation and, here again, the environment at the molecular level plays a significant role in the magnitude of interaction. Relatively few electron spin relaxation studies of solutions have been conducted and the present work is addressed toward the extension of our knowledge in this area and the retrieval of dynamical information from line shape analyses on a time scale comparable to diffusion controlled phenomena.

Specifically, the electron spin relaxation of three Mn⁺²3d⁵ complexes, Mn(CH₃CN)₆⁺², MnCl₄^-2 in acetonitrile has been studied in considerable detail. The effective spin Hamiltonian constants were carefully evaluated under a wide range of experimental conditions. Resonance widths of these Mn⁺² complexes were studied in the presence of various excess ligand ions and as a function of concentration, viscosity, temperature and frequency (X-band, ~9.5 Ԍ Hz and K-band, ~35 Ԍ Hz).

A number of interesting conclusions were drawn from these studies. For the Et₄NCl-₄^-2 system several relaxation mechanisms leading to resonance broadening were observed. One source appears to arise through spin-orbit interactions caused by modulation of the ligand field resulting from transient distortions of the complex imparted by solvent fluctuations in the immediate surroundings of the paramagnetic ion. An additional spin relaxation was assigned to the formation of ion pairs [Et₄N⁺…MnCl₄^-2] and it was possible to estimate the dissociation constant for this specie in acetonitrile.

The Bu₄NBr-MnBr₄^-2 study was considerably more interesting. As in the former case, solvent fluctuations and ion-pairing of the paramagnetic complex [Bu₄N⁺…MnBr₄^-2] provide significant relaxation for the electronic spin system. Most interesting, without doubt, is the onset of a new relaxation mechanism leading to resonance broadening which is best interpreted as chemical exchange. Thus, assuming that resonance widths were simply governed by electron spin state lifetimes, we were able to extract dynamical information from an interaction in which the initial and final states are the same

MnBr₄^-2 + Br^- = MnBr₄^-2 + Br^-.

The bimolecular rate constants were obtained at six different temperatures and their magnitudes suggested that the exchange is probably diffusion controlled with essentially a zero energy of activation. The most important source of spin relaxation in this system stems directly from dipolar interactions between the manganese 3d⁵ electrons. Moreover, the dipolar broadening is strongly frequency dependent indicating a deviation between the transverse and longitudinal relaxation times. We are led to the conclusion that the 3d⁵ spin states of ion-paired MnBr₄^-2 are significantly correlated so that dynamical processes are also entering the picture. It was possible to estimate the correlation time, ^Td, characterizing this dynamical process.

In Part II we study nuclear magnetic relaxation of bromine ions in the MnBr4-2-Bu4NBr-acetonitrile system. Essentially we monitor the 79Br and 81Br linewidths in response to the [MnBr4-2]/[Br-] ratio with the express purpose of supporting our contention that exchange is occurring between "free" bromine ions in the solvent and bromine in the first coordination sphere of the paramagnetic anion. The complexity of the system elicited a two-part study: (1) the linewidth behavior of Bu4NBr in anhydrous CH3CN in the absence of MnBr4-2 and (2) in the presence of MnBr4-2. It was concluded in study (1) that dynamical association, Bu4NBr k1= Bu4N+ + Br-, was modulating field-gradient interactions at frequencies high enough to provide an estimation of the unimolecular rate constant, k1. A comparison of the two isotopic bromine linewidth-mole fraction results led to the conclusion that quadrupole interactions provided the dominant relaxation mechanism. In study (2) the "residual" bromine linewidths for both 79Br and 81Br are clearly controlled by quadrupole interactions which appear to be modulated by very rapid dynamical processes other than molecular reorientation. We conclude that the "residual" linewidth has its origin in chemical exchange and that bromine nuclei exchange rapidly between a "free" solvated ion and the paramagnetic complex, MnBr4-2.

Joule-Thomson coefficients of propane and n-butane

Experimental Joule-Thomson measurements were made on gaseous propane at temperatures from 100 to 280˚F and at pressures from 8 to 66 psia. Joule-Thomson measurements were also made on gaseous n-butane at temperatures from 100 to 280˚ and at pressures from 8 to 42 psia. For propane, the values of these measurements ranged from 0.07986˚F/psi at 280˚F and 8.01 psia to 0.19685˚F/psi at 100˚F and 66.15 psia. For n-butane, the values ranged from 0.11031˚F/psi at 280˚F and 9.36 psia to 0.30141˚F/psi at 100˚F and 41.02 psia. The experimental values have a maximum error of 1.5 percent.

For n-butane, the measurements of this study did not agree with previous Joule-Thomson measurements made in the Laboratory in 1935. The application of a thermal-transfer correction to the previous experimental measurements would cause the two sets of data to agree. Calculated values of the Joule-Thomson coefficient from other types of p-v-t data did agree with the present measurements for n-butane.

The apparatus used to measure the experimental Joule-Thomson coefficients had a radial-flow porous thimble and was operated at pressure changes between 2.3 and 8.6 psi. The major difference between this and other Joule-Thomson apparatus was its larger weight rates of flow (up to 6 pounds per hour) at atmospheric pressure. The flow rate was shown to have an appreciable effect on non-isenthalpic Joule-Thomson measurements.

Photographic materials on pages 79-81 are essential and will not reproduced clearly on Xerox copies. Photographic copies should be ordered.

Introduction to LVFRP Technical Document 9

As stated in the title, this is an introduction to all the reports contained in this technical document and related to the various workshops on Participatory Rural Appraisal (PRA) held in all the riparian countries around Lake Victoria within the LVFRP.

On the character of the phytoplankton of the Yakimvarskii Gulf (Lake Ladoga) [Translation from: Botanicheskii Zhurnal, T. 44, No. 9, 1311-1314, 1959]

The Laboratory of Lake Studies of the Academy of Sciences of the USSR in 1956 undertook this complicated study of Lake Ladoga. The plan of the laboratory made allowance for the detailed investigation of the phytoplankton of the lake during a series of years. In the present article are given the preliminary results of observations on the phytoplankton of the Yakimvarskii Bay from 1956 to 1957. Details are also given on the concentration of dissolved gases and biogenic substances of the bay.

Record of a colloquium organised by IUBS on the methodology of radiation measurement under water. [Translation from: Mem. Inst. Ital. Idrobiol. 17, 57-79, 1964]

These minutes report on colloquium on the methodology of radiation measurement under water. The meeting was held on 3-5 January 1957, at the Biological Station, Lunz, Austria. The participants of the colloquium discussed various methodologies of radiation measurements, basic methods such as Secchi Disc and underwater photometer as well as specialist equipment like the absolute radiation apparatus.

Lq estimates for rearrangements of Fourier series

This work is concerned with estimating the upper envelopes S* of the absolute values of the partial sums of rearranged trigonometric sums. A.M. Garsia [Annals of Math. 79 (1964), 634-9] gave an estimate for the L₂ norms of the S*, averaged over all rearrangements of the original (finite) sum. This estimate enabled him to prove that the Fourier series of any function in L₂ can be rearranged so that it converges a.e. The main result of this thesis is a similar estimate of the L_q norms of the S*, for all even integers q. This holds for finite linear combinations of functions which satisfy a condition which is a generalization of orthonormality in the L₂ case. This estimate for finite sums is extended to Fourier series of L_q functions; it is shown that there are functions to which the Men’shov-Paley Theorem does not apply, but whose Fourier series can nevertheless be rearranged so that the S* of the rearranged series is in L_q.

A study of the ^9 Be nucleus

The reaction ⁷Li(³He, p)⁹Be has been used to measure excitations and intrinsic widths of levels in ⁹Be below the ⁷Li + d threshold. Previously unreported levels have been found at excitations of (13.78 ± .03) MeV and (16.671 ± .008) MeV with widths of (590 ± 60) keV and (41 ± 4) keV respectively. Two overlapping levels have been found at (11.81 ± .02) MeV and (11.29 ± .03) MeV with widths of (400 ± 30) keV and (620 ± 70) keV respectively. Branching ratios from ⁹Be levels populated in this reaction to the ground and first excited states of ⁸Be have been measured by observing the associated protons in coincidence with the decay neutrons. Branching ratios were found to be:

Excitation in ⁹Be .... Branching Ratio.......... Final Nucleus.........

(MeV) .......................... (percent) .....................................

.. 2.43 ........................... 7.5 ± 1.5 .............. ⁸Be(g.s.)

.. 3.03 ........................... 87 ± 13......................................

.. 4.65 ........................... 13 ± 4.......................................

.. 6.76 .............................. ≤ 2 ......................................

.. 11.29 ...............................≤ 2 ......................................

.. 11.81 ...............................≤ 3 ......................................

.. 6.76 ........................... .41 ≤ B.R. ≤ .69 ....... ⁸Be(2⁺)

.. 11.29 ........................... 14 ± 4 .......................................

.. 11.81 ........................... 12 ± 4 .......................................

Corresponding reduced widths for neutron emission are calculated and a comparison of the results with the expectations of current nuclear models is made. In particular the measured branching ratio to ⁸Be(g.s.) from ⁹Be(2.43 MeV) corresponds to an f-wave reduced with θ²_f = 2.1 x 10^-2, in units of ħ²/mR², with R = 4.35 fm. A comparison of this value with that predicted by a Nilsson model calculation, in which ⁹Be is taken to be a deformed nucleus, is discussed. The measured value for θ²_f is found to be consistent with that expected on the basis of measured E2-transition rates between rotational levels in ⁹Be.