Gschwend%20thesis.pdf

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o to o (\ . -. /..., ., --. o .. (a-/ÓU) aualÁX-O ro I' ~ .~ ro ~ I' ~ (\ ~ I' I' ~ I' I' W' I' ~ o~ .- i. 0 Q. ~ .. .. +- C 0 E '- Q. +- 0 K
-103- These data suggest the source of these alkylated benzenes may be related to the activities of tourists and summer residents on Cape Cod. A plot of the o-xylene data according to the day of the week in which the samples were taken clearly shows higher levels earlier in the week (figure 3-11). Separating the summer data from those of the "off season" further emphasizes this trend in the summer. Thus one may reasonably hypothesize that gasoline use by automobiles or motorboats has introduced these pollutant hydrocarbons into coastal seawater, especially during periods of intense tourism. Levels climb to about 3 times those seen during the rest of the year. Based on the plot of o-xylene concentration versus day of the week, it appears that this anthropogenic input is removed from the coastal seawater with a halflife of about l-2 days. This is consistent with the observed decline of the o-xylene levels after the Memorial Day weekend, 1978. A combination of air-sea exchange and tidal flushing may be sufficient to lower the o-xylene levels this quickly. It is also apparent from this information that the time scale of interest for these volatiles is on the order of days and not weeks. Ethyl benzene concentrations do not always appear to covary with the other alkylated benzene isomers because ethyl benzene was unresolved from another compound in the chromatograms. CI-CH4 mass spectral examination of this mixed peak in a sample acquired in February, 1978 revealed the simultaneous presence of a compound of molecular weight I08 (figure 3-12). This molecular weight assignment is assured due to presence of M + l, M + 29, and M + 41 peaks in the CI-CH4 spectrum. The m/ e 95 fragment suggests that the compound contains a terminal ethenyl group (Field, 1968), while the m/ e 93 fragment indicates the presence of a terminal. methyl substituent. It is known that the brown alga~ Fucus spp.~ utilizes - trans, cis-l,3,5-octatriene (mw 108) as its sexual chemotactic agent
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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
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 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
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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
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r . I , , I . . I · ~_. . . TEMP .
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DATE AIR MEASUREMENTS -171- o-xylen
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-173- but that direct inputs (e.g.
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-175- an atmospheric source did not
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Table 5-1. Date of collection colle
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-179- gas chromatograph equipped wi
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-181- UCON R1 Compound SE54 R1 HB51
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Release rates (ng/gm dry weight/day
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- l86- are shown in parenthese s. T
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-l88- June and September, it may be
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-190- study in some summer samples
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-192- Surprisingly, the Rhodophyta
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-194- Three deep samples (ca. 2000m
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-196- indicated that these hydrocar
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-l98- average year-round sample dat
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-200- hydrogens of the C2- and C3-b
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-202- Application of sensitive sele
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-204- tubing into round bottom flas
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-206- Figure I-I. Stripper used wit
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-208- sample. Sample water was forc
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-ZIO- ionization spectra were acqui
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. . TEMP BLAN K BEFORE SAMPLE 10m 2
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-214- Table I-i. Recoveries (%) of
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-2l6- Table 1-2. Standard deviation
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Grob Methodology -2l8- The methods
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-220- compound m & p xylenes mw 108
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-222- Table 1-4. Recoveries (ng/kg)
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-224- purchased them. Tenax may be
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-226- Appendix II. Hydrographic dat
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-229- Appendix III. Volatile organi
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94 R. P. SCHWARZENBACH, R. H. BROMU
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96 R. P. SCHWARZENBACH. R. H. BROMU
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98 R. P. SCHWARZENBACH, R. H. BROMU
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100 R. P. SCHWARZENBACH, R. H. BRoM
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102 R. P. SCHWARZENBACH, R. H. BROM
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104 Oxygeii compouiids R. P. SCHWAR
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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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