Gschwend%20thesis.pdf

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-70- Potential precursors for chemical oxidation to aldehydes are the unsaturated fatty acids. TWo of the most common fatty acids found in phytoplankton are cis-9-hexadecenoic acid and cis-9-octadecenoic acid (Ackman et al., 1968; Chuecas and Riley, 1969). Oxidation by reactants such as ozone which add to the double bond would yield only heptanal and nonanal from these compounds. It is difficult to produce octanal and decanal from such reactions, given that the appropriate fatty acids are uncommon. A second mechanism which produces all the C6-C10 aldehydes is shown in figure 2-13. This mechanism does not have to be the dominant pathway of decomposition of the fatty acids, as these adds are found in l.g/kg quantities (Jeffrey, 1966; Kattner and Brockman, 1978) while the aldehydes are found at only ng/kg levels. Side products in this reaction are omega-carboxy-aldehydes which are not volatile. The 2 fatty acids mentioned above are also found at l.gs/kg in surface slicks (Kattner and Brockman, 1978), which may be the site , of (photo?) oxidation. SUMRY Individual volatile organic compounds appear at less than 40 ng/kg in open-ocean samples from diverse areas such as the Sargasso Sea, the western Equatorial Atlantic, and the Peru upwelling region. Total volatiles for the analytical window investigated range between 10 and ioa ng/kg. These low levels may indicate: (I) insignificant sources were present, (2) rapid turnover of these organic compounds occurred, or (3) degassing to the atmos- ph ere was important. Pentadecane is present in most surface seawater samples at about LO-40 ng/kg, which is very near the calculated thermodynamic solubility (Schwarzenbach et al., 1978). This hydrocarbon may be produced from an abundant phytoplankton
-71- Figure 2-13. Mechanism for production of hexanal, heptanal, and octanal from cis-9-hexadecenoic acid. The steps are drawn out for only 1 of 'the 4 possible free radicals created by abstraction of an allylic hydrogen. i ~; l'
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VOLATILE ORGANIC COMPOUNDS IN SEAWA
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-3- concentrations were observed to
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-5- analyses. Joy Geiselman collect
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Approval Page Abstract. . . Acknowl
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Figure 2-1 2-2 2-3 2-4 2-5 2-6 2-7
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-11- 4-5 O-xylene in Vineyard Sound
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-14- background ~ the next two chap
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-16- those at room temperature. On
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-18-. Table l-l. Ha logenated volat
Page 20 and 21: -zo- They found total n-alkanes (C6
Page 22 and 23: -2Z- alpha-pinene ( ~ ), and limone
Page 24 and 25: -24- Land animals also utilize vola
Page 26 and 27: -26- importance of transport mechan
Page 28 and 29: -28- Recently, methods have been de
Page 30 and 31: -30- Figure 2-1. Station locations
Page 32 and 33: -32- A third set of seawater sample
Page 34 and 35: -34- These analyses provided a lowe
Page 36 and 37: '" ~ ~ ~ o 500 TEMPERATURE (OC) 10
Page 38 and 39: SampIe station/ depth (m) Sargasso
Page 40 and 41: NOj (PM/kg) o 10 20 30 40 chI a (Pg
Page 42 and 43: Figure 2-4. -42- o 0 . o Sections s
Page 44 and 45: -44- Figure 2-5. Sections showing n
Page 46 and 47: -46- Figure 2-6. Sections showing o
Page 48 and 49: -48- Figure 2-7. Sections showing i
Page 50 and 51: -50- and l49 (M+41) ions in the CH4
Page 52 and 53: ~ ~ ~ ~ ii "' ~ ï: "' l¡ Q: 3(' 5
Page 54 and 55: -54- A family of straight chain ald
Page 56 and 57: o 10 6 6.0 100 3.2 1000 . 2.2 0 9.2
Page 58 and 59: -58- Equatorial Atlantic, does not
Page 60 and 61: -60- Zsolnay (l973, 1976) has repor
Page 62 and 63: netS 40 (ng/kg) 20 +24/7 +15/7 30 2
Page 65 and 66: sample was enriched relative to adj
Page 67 and 68: -67- On the other hand, a phytoplan
Page 69: °2 (m//kg) 2 6 . . . . 4 . . . . .
Page 73 and 74: -73- fatty acid, hexadecanoic acid,
Page 75 and 76: -75- In addition, the Cape, and the
Page 77 and 78: ::.',:.:' 71° 70° 69° 68° 67°W
Page 79 and 80: -79- Figure 3-2. Recirculating stri
Page 81 and 82: -81- o (heated to 60 C to reduce th
Page 83 and 84: VOLATILE EXTRACTION ref. Grab and Z
Page 85 and 86: RESULTS AND DISCUSSION Hydrographic
Page 88 and 89: -88- Figure 3-5. Salinity (0/00) ve
Page 90 and 91: -90- revealing the variation of sal
Page 92 and 93: .. 1.5 ..E0 1.0 - Ci ci :: 0.5 II'
Page 94 and 95: -94- Figure 3-7. Chlorophyll ~ (~g/
Page 96 and 97: -96- Three known incidents of hydro
Page 98 and 99: ~ ( ng/kg) 40 30 20 ._... ~ ? 1 0 .
Page 100 and 101: ~ 4 2 ( ng/kg) o '-+~ ( ng/kg) ~ (
Page 102 and 103: o to o (\ . -. /..., ., --. o .. (a
Page 104 and 105: -104- Figure 3-11. O-xylene concent
Page 106 and 107: -106- Figure 3-12. Electron impact
Page 108 and 109: -108- (Müller and Jaenicke, 1973).
Page 110 and 111: 30 20 UNKNOWN m.w. 108 10 (ng/kg) o
Page 112 and 113: -112- Figure 3-14. Naphthalene and
Page 114 and 115: -114- The naphthalene-to-methyl nap
Page 117 and 118: -117- with 0.29 for o-xylene and 0.
Page 119 and 120: nC14 15 10 (ng/kg) 5 o 80 60 n C 15
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"ep¡" 50 40 30 20 10 s...." . . \~
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-123- Figure 3-18. C6-CiO aldehyde
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Figure 3-19. -125- Heptanal concent
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-127- production by the plankton or
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20 18 2 16 ~ "- 14 3 3 3 :- 12 3/ 2
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tf 10-' ~ ~ ct ~ ~ ~ ~ '" .. ~ ~ ~
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15 DMDS (ng/kg) 5 o 35 30 25 DMTS 2
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-135- polysulfide volatiles. Partic
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TOTAL VC (ng/kg) 500 400 300 200 10
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-139- This suggested an anthropogen
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"Also, short range transport and de
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-143- were conducted. Rain samples
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Short-term Temporal Studies. -145-
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40r RAIN RAIN 124 ~ 0 \ . MORNING (
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-149- Figure 4-2. Relative C2- and
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-151- Finally, the diesel-exhause-d
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Figure 4-3. Ratios of C2- and sampl
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Figure 4-4. Salini ty CD taken velo
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-157- Figure 4-5. O-xylene concentr
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-l59- while at other times they wer
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CDsw CDsw 11/10/77 11/22/77 CDsw 10
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-163- Figure 4-6. a-xylene concentr
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-165- The Quashnet River and Sippew
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Sippewissett Quashnet CD Marsh CD C
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r . I , , I . . I · ~_. . . TEMP .
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DATE AIR MEASUREMENTS -171- o-xylen
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-173- but that direct inputs (e.g.
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-175- an atmospheric source did not
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Table 5-1. Date of collection colle
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-179- gas chromatograph equipped wi
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-181- UCON R1 Compound SE54 R1 HB51
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Release rates (ng/gm dry weight/day
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- l86- are shown in parenthese s. T
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-l88- June and September, it may be
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-190- study in some summer samples
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-192- Surprisingly, the Rhodophyta
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-194- Three deep samples (ca. 2000m
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-196- indicated that these hydrocar
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-l98- average year-round sample dat
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-200- hydrogens of the C2- and C3-b
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-202- Application of sensitive sele
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-204- tubing into round bottom flas
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-206- Figure I-I. Stripper used wit
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-208- sample. Sample water was forc
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-ZIO- ionization spectra were acqui
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. . TEMP BLAN K BEFORE SAMPLE 10m 2
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-214- Table I-i. Recoveries (%) of
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-2l6- Table 1-2. Standard deviation
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Grob Methodology -2l8- The methods
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-220- compound m & p xylenes mw 108
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-222- Table 1-4. Recoveries (ng/kg)
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-224- purchased them. Tenax may be
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-226- Appendix II. Hydrographic dat
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-229- Appendix III. Volatile organi
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94 R. P. SCHWARZENBACH, R. H. BROMU
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96 R. P. SCHWARZENBACH. R. H. BROMU
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98 R. P. SCHWARZENBACH, R. H. BROMU
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100 R. P. SCHWARZENBACH, R. H. BRoM
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102 R. P. SCHWARZENBACH, R. H. BROM
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104 Oxygeii compouiids R. P. SCHWAR
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106 R. P. SCHWAKZENRACH. R. H. BROM
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-245- Appendix iv. Physical chemica
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-247- Appendix V. Mass spectra of s
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IS N L~ N r IS N ~Ð :i ,E -i Ji: "
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LD~ E) E) (Y E) LD E) LD N X E) in
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il .. E) N X I E) E) (Y E) il N E)
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CD CD .. r. L. - N ~-'._-----'-----
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E) i N f f ( -455 .- N ~ r t ì igN
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E) E) ~i !D i N --- J -lri r~ 18 r~
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REFERENCES Ackman, R.G., C. S. Toch
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. Cleveland, W. S., B. air pollutio
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-264- Grob, K. and F. ZUrcher. (l97
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-266- Lee, C. and J.L. Bada. (1975)
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-268- N. A. S. (1975a) Assessing Po
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-270- Strickland, J.D .R. and T .R.
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