Gschwend%20thesis.pdf

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-202- Application of sensitive selective detectors (e.g. electron capture detector) may reveal many additional natural (e.g. haloterpenes) and anthropogenic (e. g. chlorobenzenes) compounds in seawater.
APPENDIX I ANALYTICAL METHODS USED FOR THE DETERMINATION OF VOLATILE ORGANIC COMPOUNDS IN SEAWATER Introduction This appendix describes the methods used for the analysis of volatile organic compounds in seawater. These stripping methods have been adapted from others reported in the literature ("Tenax": Zlatkis et aL., 1973; Novotny et al., 1974; Bellar and Lichtenberg, 1974; Bertsch et al., 1975; May et al., 1975; "Grob": Grob, 1973; Grob and ZUrcher, 1976). Experiments performed to evaluate the methods will also be described. Finally, a brief discussion of the relative merits of these methodological approaches will be provided. Sampling PVC Niskins (5- and 30-liter) with stainless steel or Teflon-coated springs were used to collect seawater samples. The bottles were flushed with tapwater and then extensively rinsed at sea before use. Bottles were stored closed on deck. A comparison of the volatile organic compounds in surface seawater samples collected with a 5-liter glass round bottom flask and a PVC Niskin did not reveal any differences. This was also seen for coastal seawater samples (Schwarzenbach et al., 1978). Sampling was always performed with the winds blowing off the sea and onto the side of the ship with the hydroplatform. On the Sargasso Sea cruise, water samples were transferred through the air into round bottom flRsks. For the western Equatorial Atlantic samples, water was transferred from the Niskin samplers through glass -Z03-
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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
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 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
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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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