Gschwend%20thesis.pdf

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o 10 6 6.0 100 3.2 1000 . 2.2 0 9.2 5 -. ~ ~ 10 8.4 3.6 5 ~ 100 2.1 1000 1.4 0 2.9 10 .4.2 100 2,2 1000 1.4 I o i 10km STAT/ON NUMBER 5 4 3 2 2.5 6.3 ~ 4.6 3.9 -4.5 2.5 3.5 4.0 3.5... ........ ~..~ t.:,);::~;;,,\~'n;;~ 2.4 . ".::;:::...:.\.:. '::" : '.: . . . ...~:';::';:~:,,:: .... .' HEXANAL CONCS. (ng/kg) 5.4 6.8~ 3.3 2.0 2.2 2.0 2.9 . 3.5 .:.:::.Q: 2.4 .4:~\':: 0.9 . ,,'f./:,y:f(: ::'.:: t,6 ...::.g.::.:'~':":.'.: . ......,..:::.::::..:.... . :. . HEPTANAL CONCS. (ng/kg) 3.9 2.8 .3.2 2.3 2.0 ~ 1 2.1 ~ 1 . . l . l .,,",(~:,,:(t/':\~'!;: " l .:..: .. .' '. . '" .;:::.t:~::'..~ : '.. . .' 2.3 ,'f::.:.~'~~(Y;~::'~".':':óciANAL' CONës. ..... .... (ng/kg)
-57- approaches to the study of organic matter in the sea have previously suggested the importance of this phenomenom. Menzel (1975), in his review of organic matter in the sea, has speculated that DOC is rapidly decomposed after pulse inputs since only poor correlation with measured primary productivity and DOC values could be found. Obser- vations on specific organic metabolites such as amino acids (Lee and Bada, 1975) have also led investigators to conclude that these compounds are quickly removed af ter release in to seawater. Thus, it appears that the concentrations of some biochemically labile materials may be controlled in seawater by heterotrophic activity. Volatile compounds, whose principal source is production in surface seawater, have an additional sink from seawater in transport into the atmosphere. The mixed layer of the open ocean is degassed with a residence time of about i month (Broecker and Peng, 1974). Therefore, unless sources in the mixed layer continually produce a volatile organic compound, this atmospheric sink will rapidly deplete the individual volatile organic compound concentrations to values in equilibrium with the atmosphere. The total volatile fraction found in the Sargasso Sea and the Peru upwelling region samples comprises less than O. OL% of the DOC. Specific Volatiles: ,Pentadecane Pentadecane was the best-studied volatile compound. It was ubiquitous in surface seawater samples at a concentration near its calculated thermodynamic solubility (Schwarzenbach et aL., 1978). The lack of other homologues (e. g., tetradecane and hexadecane) indicates that this compound was not derived from a fossil fuel source. Land derived dust, for example, from the region of the
Page 1 and 2:
VOLATILE ORGANIC COMPOUNDS IN SEAWA
Page 3 and 4:
-3- concentrations were observed to
Page 5 and 6: -5- analyses. Joy Geiselman collect
Page 7 and 8: Approval Page Abstract. . . Acknowl
Page 9 and 10: Figure 2-1 2-2 2-3 2-4 2-5 2-6 2-7
Page 11: -11- 4-5 O-xylene in Vineyard Sound
Page 14 and 15: -14- background ~ the next two chap
Page 16 and 17: -16- those at room temperature. On
Page 18 and 19: -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 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 and 70: °2 (m//kg) 2 6 . . . . 4 . . . . .
Page 71 and 72: -71- Figure 2-13. Mechanism for pro
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).
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30 20 UNKNOWN m.w. 108 10 (ng/kg) o
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-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.
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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
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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
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tf 10-' ~ ~ ct ~ ~ ~ ~ '" .. ~ ~ ~
Page 133 and 134:
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
Page 145 and 146:
Short-term Temporal Studies. -145-
Page 147 and 148:
40r RAIN RAIN 124 ~ 0 \ . MORNING (
Page 149 and 150:
-149- Figure 4-2. Relative C2- and
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
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-173- but that direct inputs (e.g.
Page 175 and 176:
-175- an atmospheric source did not
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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 210 and 211:
-ZIO- ionization spectra were acqui
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
Page 263 and 264:
. Cleveland, W. S., B. air pollutio
Page 265 and 266:
-264- Grob, K. and F. ZUrcher. (l97
Page 267 and 268:
-266- Lee, C. and J.L. Bada. (1975)
Page 269 and 270:
-268- N. A. S. (1975a) Assessing Po
Page 271 and 272:
-270- Strickland, J.D .R. and T .R.
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