Gschwend%20thesis.pdf

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4 GASOLINE GASOLI NE/OI L FOR OUTBOARD 3 2 0 !. 2 . . . 4 AUTO EXHAUST SEPT. 2, 1978 SKI BOATS 3 ~ . ~ 1 ~ Q: 0 oq ~ 4 - AUTO EXHAUST OUTBOARD EXHAUST DISSOLVED DISSOLVED .. oq 3 IN SEAWATER IN SEAWATER ¡¡ Q: 2 . . . 0 4 3 2 0 01 ESEL EXHAUST FUEL 01 L DISSOLVED IN SEAWATER . . . . .
-151- Finally, the diesel-exhause-dissolved-in-seawater pattern differs from the gasoline-exhaust-dissolved-in-seawater pattern in that the former showed Cz- and C3-benzenes at similar levels while the latter had relatively more C2- than C3-benzenes. This is probably due to the relatively facile transfer of C2-benzenes on the one hand, and to the original enrichment of C3 -benzenes in the heavier diesel on the other hand. This C3 ~benzene enrichment is particularly evident for l, 2, 3-trimethyl benzene relative to the other lower-boiling isomers. The average year-round isomer distribution is indicated by the dots in figure 4-2 and most resembles the patterns for auto-exhaust~dissolved-in- seawater and September 2 boat exhaust at CD. The linear correlation coeffi- cients for the isomer distributions found in the lab studies versus the average year-round, Idistribution values were: gasoline, O. 9l; auto exhaus t, 0.46; auto exhaust dissolved in seawater, 0.95; gasoline/oil for outboards, 0.88; outboard exhaust dissolved in seawater, 0.61; Sept. 2, 1978 ski boats, 0.94; diesel exhaust dissolved in seawater, 0.80; and #2 fuel oil, 0.44. The most notable discrepancies in these distributions are found for the peaks containing para substituents (para-xylene, p-ethyl methyl benzene, and 1,2, 4-trimethyl benz ene; the first 2 were not resolved from the meta isomers by GC and appear as a single peak in the isomer distributions) . These compounds were found to be the most rapidly degraded of the. alkylated benzenes by Kappeler (1976) in his studies of the microbial degradation of the alkyla ted benzenes in groundwater. Thus, the discrepancies may reveal the importance of a similar biochemical degradation in these coastal seawaters. Utilizing o-xylene as an internal standard, the other C2- and C3- benzenes may be studied for their relative variations during the year
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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
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-zo- They found total n-alkanes (C6
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-2Z- alpha-pinene ( ~ ), and limone
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-24- Land animals also utilize vola
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-26- importance of transport mechan
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-28- Recently, methods have been de
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-30- Figure 2-1. Station locations
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-32- A third set of seawater sample
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-34- These analyses provided a lowe
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'" ~ ~ ~ o 500 TEMPERATURE (OC) 10
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SampIe station/ depth (m) Sargasso
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NOj (PM/kg) o 10 20 30 40 chI a (Pg
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Figure 2-4. -42- o 0 . o Sections s
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-44- Figure 2-5. Sections showing n
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-46- Figure 2-6. Sections showing o
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-48- Figure 2-7. Sections showing i
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-50- and l49 (M+41) ions in the CH4
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~ ~ ~ ~ ii "' ~ ï: "' l¡ Q: 3(' 5
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-54- A family of straight chain ald
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o 10 6 6.0 100 3.2 1000 . 2.2 0 9.2
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-58- Equatorial Atlantic, does not
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-60- Zsolnay (l973, 1976) has repor
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netS 40 (ng/kg) 20 +24/7 +15/7 30 2
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sample was enriched relative to adj
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-67- On the other hand, a phytoplan
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°2 (m//kg) 2 6 . . . . 4 . . . . .
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-71- Figure 2-13. Mechanism for pro
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-73- fatty acid, hexadecanoic acid,
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-75- In addition, the Cape, and the
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::.',:.:' 71° 70° 69° 68° 67°W
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-79- Figure 3-2. Recirculating stri
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-81- o (heated to 60 C to reduce th
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VOLATILE EXTRACTION ref. Grab and Z
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RESULTS AND DISCUSSION Hydrographic
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-88- Figure 3-5. Salinity (0/00) ve
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-90- revealing the variation of sal
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.. 1.5 ..E0 1.0 - Ci ci :: 0.5 II'
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-94- Figure 3-7. Chlorophyll ~ (~g/
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-96- Three known incidents of hydro
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~ ( 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
Page 121 and 122: "ep¡" 50 40 30 20 10 s...." . . \~
Page 123 and 124: -123- Figure 3-18. C6-CiO aldehyde
Page 125 and 126: Figure 3-19. -125- Heptanal concent
Page 127 and 128: -127- production by the plankton or
Page 129 and 130: 20 18 2 16 ~ "- 14 3 3 3 :- 12 3/ 2
Page 131 and 132: tf 10-' ~ ~ ct ~ ~ ~ ~ '" .. ~ ~ ~
Page 133 and 134: 15 DMDS (ng/kg) 5 o 35 30 25 DMTS 2
Page 135 and 136: -135- polysulfide volatiles. Partic
Page 137 and 138: TOTAL VC (ng/kg) 500 400 300 200 10
Page 139 and 140: -139- This suggested an anthropogen
Page 141 and 142: "Also, short range transport and de
Page 143 and 144: -143- were conducted. Rain samples
Page 145 and 146: Short-term Temporal Studies. -145-
Page 147 and 148: 40r RAIN RAIN 124 ~ 0 \ . MORNING (
Page 149: -149- Figure 4-2. Relative C2- and
Page 153 and 154: Figure 4-3. Ratios of C2- and sampl
Page 155 and 156: Figure 4-4. Salini ty CD taken velo
Page 157 and 158: -157- Figure 4-5. O-xylene concentr
Page 159 and 160: -l59- while at other times they wer
Page 161 and 162: CDsw CDsw 11/10/77 11/22/77 CDsw 10
Page 163 and 164: -163- Figure 4-6. a-xylene concentr
Page 165 and 166: -165- The Quashnet River and Sippew
Page 167 and 168: Sippewissett Quashnet CD Marsh CD C
Page 169 and 170: r . I , , I . . I · ~_. . . TEMP .
Page 171 and 172: DATE AIR MEASUREMENTS -171- o-xylen
Page 173 and 174: -173- but that direct inputs (e.g.
Page 175 and 176: -175- an atmospheric source did not
Page 177 and 178: Table 5-1. Date of collection colle
Page 179 and 180: -179- gas chromatograph equipped wi
Page 181 and 182: -181- UCON R1 Compound SE54 R1 HB51
Page 183 and 184: Release rates (ng/gm dry weight/day
Page 186 and 187: - l86- are shown in parenthese s. T
Page 188 and 189: -l88- June and September, it may be
Page 190 and 191: -190- study in some summer samples
Page 192 and 193: -192- Surprisingly, the Rhodophyta
Page 194 and 195: -194- Three deep samples (ca. 2000m
Page 196 and 197: -196- indicated that these hydrocar
Page 198 and 199: -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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