Gschwend%20thesis.pdf

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-50- and l49 (M+41) ions in the CH4 chemical ionization (CI) spectrum and m/e 108 in the electron impact (El) spectrum (figure 2-8). Loss of l3 and 27 mass units (giving m/e 95 and 81) in the CI spectrum indicates the presence of a terminal ethenyl group (Field, 1968), while loss of 15 mass units (giving m/e 93) in both the EI and CI spectra suggests that there is a terminal methyl substituent also. Due to insufficient sample size, the remainder of the EI spectrum was largely uninter- pretable. Authentic trans ,cis-I, 3 ,5-octatriene and ethyl benzene CI spectra are also shown in figure 2-8. These spectra have all the same major fragment peaks as the unknown and èthyl benzene mixture in the sample. However, since this octatriene does not coelute with ethyl benzene, the unknown cannot be this particular isomer. Al though not all cyclic and branched structures can be ruled out, these data are consistent with a structure such as a straight chain octatriene. The GC peak heights of this unknown compound (ro 108) were estimated by subtracting assumed ethyl benzene peak heights from that of the mixed GC peak. The ethyl benzene peak heights were obtained by assuming that they were proportional to the peak heights of the other C2-benzene isomers. This was reasonable because ethyl benzene levels covary with the other C2-benzene isomer concentrations in most fossil fuels and environmental samples tested (chapter 4). These difference estimates agree well with predicted peak heights based on GCMS where data were available. The resultant spatial distribution of the concentration of this unknown compound (ro 108) is shown in figure 2-7. Maximum values were always found near the surface. Station 3 showed the highest level of all surface samples ând the concentrations decreased in the offshore direction.
-51- Figure 2-8. Electron impact (EI) and methane chemical ionization (CI) mass spectra of unknown compound (mixed with ethyl benzene) isolated from seawater samples collected in the Peru upwelling region. Also shown are CI spectra from authentic trans, cis-l,3 ,5-octatriene and ethyl benzene. Fragments from m/e 76 to 79 were not collected in the sample spectra because of solvent (CS2) interference. M/E values greater than 120 are amplified 4 times in the CI spectra of the Peru sample and trans, cis-I, 3, 5-octatriene.
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 52 and 53: ~ ~ ~ ~ ii "' ~ ï: "' l¡ Q: 3(' 5
Page 54 and 55: -54- A family of straight chain ald
Page 56 and 57: o 10 6 6.0 100 3.2 1000 . 2.2 0 9.2
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).
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 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 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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