Gschwend%20thesis.pdf

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-194- Three deep samples (ca. 2000m) contained high concentrations of pentadecane. In situ production or vertical transport and release at depth do not seem likely to be the source of this hydrocarbon occurrence. Advective transport of North Atlantic Deep water may have carried this fairly stable organic compound from the biologically productive surface formation sites to the deep ocean. C2-benzenes were found in the recently upwelled surface water off Peru. Concentrations of meta + para xylene were about 4 ng/kg at 5 and 20m, about 3 ng/kg at lOOm, and about 2 ng/kg or less in the deeper samples. This distribution indicates a surface or atmospheric source. The air concentration necessary for the atmosphere to have been a source was l-2 ng/l-air. Vertical transport of m + p xylenes was indicated by the anomalously low concentrations of these aromatic hydrocarbons in 5- and 20-m sample~ at stations 4 and 5 off Peru and by an unusually high concentration of these compounds in seawater collected near the bottom at station 4. Low nutrient concentrations in these surface seawaters revealed that intense phytoplankton production had occurred, and if the m + p xylenes became associated with biogenic particulate matter, subsequent sedimentation and remineralization near the bottom may have introduced these compounds to deep wa ter . An unidentified alkene (ro 108) was recovered at up to 30 ng/kg from surface seawater samples from the upwelling region off Peru. The GC retention index and mass spectra of this compound showed that it is probably structurally related to fucoserraten, an unsaturated hydrocarbon used by the benthic alga, Fucus, as a sexual chemotactic signal. The unknown compound may be formed by isomerization of fucoserraten (trans,
Coastal Seawater -195- Total volatile concentrations found in a study of coastal seawater were between 200 and 500 ng/kg. Higher total concentrations coincided with the late-winter phytoplankton bloom. Anthropogenic inputs of hydrocarbons caused similarly high total concentrations. All of the C13-C17 alkanes and pristane were found at relatively higher concentrations after a nearby oil spill. The "carbon preference index" was near i at that time and corroborated the assignment of these compounds to a fossil fuel source. Pentadecane and heptadecane showed separate large concentration increases up to 80 and 20 ng/kg, respectively, in the sumer. The high "carbon preference index" associated with these concentration maxima
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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
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 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
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 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
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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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