Gschwend%20thesis.pdf

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-96- Three known incidents of hydrocarbon spills occurred in the region during the study period. In January, 1977 a barge carrying Bouchard no. 2 fuel oil spilled part of its cargo at the head of Buzzards Bay (ca. 16 km. from CD). Some time later.. ice ~ laden with some of this oil, was observed in the waters near CD. Also, in March, 1978 a large gasoline spill occurred near Block Island in Long Island Sound (ca. 80 km. from CD). Finall~ in April of 1978, a second barge spilled oil near the west end of the Cape Cod Canal (ca. l6 km. from CD). Only the first of these accidents could be clearly related to the level of volatile organic compounds at CD (see below and Schwarzenbach et al., 1978) . Variations of Volatile Organic Compounds Alkylated Benzenes. The seasonal changes in the concentrations of the C2- and C3-alkylated benzenes are shown in figures 3-8 and 3-9. All of these compounds, except ethyl benzene (see later discussion), closely covary. The C2-benzenes usually appear at an isomer ratio of ethyl benzene: m + p-xylenes: o-xylene = 1: 2: I. These isomers were always more abundant than the C3-benzenes. Still more highly substituted benzenes were also observed at lower concentrations and their temporal distribu- tions parallel those of the lower homologues. In order to demonstrate the nature of a source of the alkylated benzenes, one of them, o-xylene (or mOLe properly, I, 2-dimethyl benzene) has been replotted including three samples taken the three days immedi~ ately following the Memorial Day weekend (May 27-29, 1978) (figure 3-l0). One can see a tremendous fluctuation in the concentration of this compound at this time over a very short time interval. Indeed, the sample following the weekend shows the highest concentration found all year.
-97- Figure 3-8. C2-benzenes (nglkg) in biweekly seawater samples from CD. Question marks indicate samples in which ethyl benzene coeluted with an unknown compound. The open circle shows ethyl benzene concentration found when volatiles were chromatographed on a column which resolved these compounds.
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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
Page 46 and 47: -46- Figure 2-6. Sections showing o
Page 48 and 49: -48- Figure 2-7. Sections showing i
Page 50 and 51: -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 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-
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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
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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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