Gschwend%20thesis.pdf

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-220- compound m & p xylenes mw 108 nC15 hexanal heptanal octanal sample (stn/ depth) treatment 6/1000 tr tr tr 1. 7 tr tr 6/1 OOOP tr tr tr 1.8 tr tr 6/1000FP tr tr tr 2.2 tr 2.2 5/900 tr tr tr tt tr tr 5/900P tr tr tr tr- tr tr 5/900FP tr tr 3.5 2.4 tr 2.3 2/5P 4.5 9.3 21. 8 10.0 9.9 4.5 2/5 FP 4.3 4.7 13.4 4.6 3.3 2.3 3/20P 2.9 2.5 14.9 3.9 3.2 2.0 3/20FP 2.7 2.7 10.1 3.5 2.9 3.3 4/340P tr tr tr tr tr tr 4/340FP 6.8 tr tr tr tr tr 5/5P 3.0 22.2 8.3 9.9 9.5 6.2 5/5 FP 2.8 18.4 10.3 ó.3 5.4 3.9 tr: trace (less than 2 ng/kg or 10% of the I. S.) F: filtered P: poisoned
-221- glass fiber filtered by gravity into six 2-liter reagent flasks, poisoned with mercuric chloride, and spiked with compounds exhibiting the same func- tionality as those found in the Peru samples but with carbon skeletons not seen in coastal seawater. Three of these samples were analyzed immediately, while the other 3 were sealed in styrofoam chests and stored at 4°C for i month (as were the cruise samples). At the end of that time, the samples were analyzed and the resultant recoveries for the spiked compounds compared to those exhibited by the unstored samples (Table 1-4). The three hydrocarbons, an alkane, an olefin, and an aromatic, all showed approximately 60% relative recovery at 1.5 times greater efficiency than a month earlier. Each tripli- cate set showed less than 20% variation of these results. The decreased recoveries of the hydrocarbons after storage may be due to their removal from solution, i. e., a stripable state. Possibly these compounds were adsorbed onto the walls of the glass flask (Kaiser, 1971) or were incorporated into newly formed particulate matter (Riley, 1970). In keeping with this, the more sgluble the hydrocarbon, the greater was its relative recovery af ter storage. On the other hand, 2-ethyl hexanal is relatively very solubl~ and may be unaffected by these processes. In fact, these changes may have increased the proportion of this compound in a stripable state and thus accounted for the improved recovery after storage. Comparison of Tenax and Grob Methods The Tenax method offers several advantages. First, it is much faster and is the only one capable of handling numerous samples as they are returned from hydrocasts. Next, the traps are easy to prepare. It is diff icul t to construct the charcoal traps of Grob, and we have always
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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
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-l59- while at other times they wer
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CDsw CDsw 11/10/77 11/22/77 CDsw 10
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-163- Figure 4-6. a-xylene concentr
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-165- The Quashnet River and Sippew
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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 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 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
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-270- Strickland, J.D .R. and T .R.
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