Gschwend%20thesis.pdf

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-148- in a glass flask, stripped onto a charcoal trap, extracted into methylene chloride, and analyzed by GC. In another experiment, auto and diesel exhaust were collected in empty glass flasks, Each was connected by a U- shaped neck to an identical flask containing thoroughly prestripped seawater (gently stirred). The vapors were then allowed to exchange between the air and the seawater for i day. The water was then analyzed for C2... and C3-. benzenes. In order to study the effects of outboard engines, water was collected near the underwater exhaust of an outboard engine, and this was analyzed for its isomer distribution. Also, a seawater sample was collected at CD on September 2 during an afternoon of continual motorboat activity in the immediate vicinity of CD. The resultant isomer distributions are shown in figure 4-2. Although all of the patterns are similar, some important differences exist. Gasoline and gasoline/oil for motorboats contain less C3-benzenes than .the heavier fuel oil. Auto exhaust and outboard-exhaust-dissolved-in- seawater have similar isomer distributions. This may be explained if both engines produced like exhaust patterns, and this pattern is not changed on transfer .into seawater bv underwater exhaust systems of outboard engines. The isomer distribution obtained from exchange of auto exhaust vapor wi th seawater differs from that of the original exhaust by an enrichment in the lower-boiling compounds. The pattern of auto-exhaust-dissolved-in~ seawater resembles that observed in CD sample of September 2. This may be due to boats operating near the dock that had either inboard ör inboardloutboard engines. These powerboat types exhaust directly into the atmosphere, a situation simulated in the lab by placing exhaust gases in close proximity to seawater and allowing them to dissolve.
-149- Figure 4-2. Relative C2- and C3-benzene isomer abundances from several fuels , auto exhaust, and some exhausts dissolved in seawater. Abundances are normalized so that o-xylene (1, 2-dimethyl benzene) equals 1. Closed circles show average relative abundances from biweekly seawater samples from CD. '-
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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
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
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: 40r RAIN RAIN 124 ~ 0 \ . MORNING (
Page 151 and 152: -151- Finally, the diesel-exhause-d
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
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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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