Gschwend%20thesis.pdf

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-ZIO- ionization spectra were acquired using CH4 as the reactant gas at 950 ~ o pressure, with the ionization chamber at about 180 C and 130 eV ionization potentiaL. Evalua tion of the Method Blanks were determined throughout the cruises. Precleaned Tenax traps were placed on the helium~flushed empty stripper. Helium purging was begun, as if the seawater sample were in place, and continued for 5 minutes. At the end of this time the trap was removed -to a screw- cap vial and stored in the freezer along with other sample traps until GC analysis. Typical gas chromatograms for blanks (no standards added) and open ocean seawater samples are shown in figure i-Z. The blank chromatogram was very similar to that shown previously by May et al. (1975) . Contamination peaks were present in the "solvent regionll (pentan~ acetone, methylene chloride) and for this reason, and because the resolution in this region of the chromatogram was poor, this part of the gas chromatograms was subsequently ignored. Peaks were also present near the high-boiling end of the chromatogram, but these elute beyond the volatile compounds Qoncentrated by stripping. A large and variable blank was found for the western Equatorial Atlantic samples. Identification of the compounds found in this contamination showed the presence of several unusual compounds which were stored in the same refrigerator as the Tenax traps. Traps stored in more than one refrigerator before GC analysis showed contamination from compounds unique to each refrigerator. Thus f Tenax trap storage in the screw-cap vials was not always adequate for the prevention of large blanks.
-2ll- Figure 1-2. Gas chromatograms showing volatile compounds collected with Tenax method from IO m and 100 m seawater samples at a station southeast of Bermuda in February, 1977. Gas chromatograms from blank analyses run before and after the samples are also shown. Closed circles indicate the l-chloro-n-alkane internal standards (6, 10,12) which were added to the water at 10 ng/kg. For gas chromatography conditions see text.
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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 .
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~ 4 2 ( ng/kg) o '-+~ ( ng/kg) ~ (
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o to o (\ . -. /..., ., --. o .. (a
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-104- Figure 3-11. O-xylene concent
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-106- Figure 3-12. Electron impact
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-108- (Müller and Jaenicke, 1973).
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30 20 UNKNOWN m.w. 108 10 (ng/kg) o
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-112- Figure 3-14. Naphthalene and
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-114- The naphthalene-to-methyl nap
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-117- with 0.29 for o-xylene and 0.
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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
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
Page 200 and 201: -200- hydrogens of the C2- and C3-b
Page 202 and 203: -202- Application of sensitive sele
Page 204 and 205: -204- tubing into round bottom flas
Page 206 and 207: -206- Figure I-I. Stripper used wit
Page 208 and 209: -208- sample. Sample water was forc
Page 212 and 213: . . TEMP BLAN K BEFORE SAMPLE 10m 2
Page 214 and 215: -214- Table I-i. Recoveries (%) of
Page 216 and 217: -2l6- Table 1-2. Standard deviation
Page 218 and 219: Grob Methodology -2l8- The methods
Page 220 and 221: -220- compound m & p xylenes mw 108
Page 222 and 223: -222- Table 1-4. Recoveries (ng/kg)
Page 224 and 225: -224- purchased them. Tenax may be
Page 226 and 227: -226- Appendix II. Hydrographic dat
Page 229 and 230: -229- Appendix III. Volatile organi
Page 231 and 232: 94 R. P. SCHWARZENBACH, R. H. BROMU
Page 233 and 234: 96 R. P. SCHWARZENBACH. R. H. BROMU
Page 235 and 236: 98 R. P. SCHWARZENBACH, R. H. BROMU
Page 237 and 238: 100 R. P. SCHWARZENBACH, R. H. BRoM
Page 239 and 240: 102 R. P. SCHWARZENBACH, R. H. BROM
Page 241 and 242: 104 Oxygeii compouiids R. P. SCHWAR
Page 243 and 244: 106 R. P. SCHWAKZENRACH. R. H. BROM
Page 245 and 246: -245- Appendix iv. Physical chemica
Page 247 and 248: -247- Appendix V. Mass spectra of s
Page 249 and 250: IS N L~ N r IS N ~Ð :i ,E -i Ji: "
Page 251 and 252: LD~ E) E) (Y E) LD E) LD N X E) in
Page 253 and 254: il .. E) N X I E) E) (Y E) il N E)
Page 255 and 256: CD CD .. r. L. - N ~-'._-----'-----
Page 257 and 258: E) i N f f ( -455 .- N ~ r t ì igN
Page 259 and 260: E) E) ~i !D i N --- J -lri r~ 18 r~
Page 261 and 262:
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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