Chemical Geology (Isotope Geoscience Section), 101 (1992) 223-233 223 Elsevier Science Publishers B.V., Amsterdam Stable carbon isotope variations in sediment from Baffin Bay, Texas, U.S.A.: Evidence for cyclic changes in organic matter source Brian Anderson, R.S. Scalan, E.Wm. Behrens" and P.L. Parker Marine Science Institute, The University of Texas at Austin, Port Aransas, TX 78373, USA (Revised and accepted May 23, 1991 ) ABSTRACT Anderson, B., Scalan, R.S., Behrens, E.Wm. and Parker, P.L., 1992. Stable carbon isotope variations in sediment from Baffin Bay, Texas, U.S.A.: Evidence for cyclic changes in organic matter source. In: S.A. Macko and M.H. Engel (GuestEditors), Isotope Fractionations in Organic Matter: Biosynthetic and Diagenetic Processes. Chem. Geol. (Isot. Geosci. Sec. ), 101: 223-233. Baffin Bay, Texas, a drowned Pleistocene river valley, is filled with up to 20 m of exceptionally well-preserved Holocene and recent sediments. Piston cores from the upper 4 m have been described and analyzed for elemental composition and t~'3C of the total organic carbon and carbonate. Strong cyclic patterns were observed for all of these parameters. The total organic carbon (TOC) level varied between 1% and 6%. (C/N ratios varied between l0 and 14. 8'3C showed a cyclicity with depth and a slight shift toward more positive values with dep,hs. These variations are interpreted as being due to different relative inputs of seagrass (5 ' 3C - = 10% ) and phytoplankton (g 13C _ ~, 20%0 ) to the sediment. The cores contained fine-grained carbonate and some massive dolomite, t~' 3C of the carbonate varied between - 3% and + 1o/o0except for two more positive values. The lack of a trend toward light carbonate with depth was taken to mean that little ( < 5%) CO2 from the oxidation of organic matter is present in the carbonates. Overall the changes in the relative intensity of these sources is thought to reflect regional climatic and weathering cycles. 1. Introduction The Laguna Madre of Texas is a shallow estuarine system bounded by the mainland and by a barrier island, Padre Island (Fig. l ). The Laguna Madre stretches from Corpus Christi Bay to the Rio Grande River. Despite the fact that the Laguna has historically been hypersaline, with salinities commonly of 45-65 ppt and rarely of 85 ppt, it is highly productive (Hedgepeth, 1953; Odum and Wilson, 1962; Behrens, 1966). More than 105 ha of seagrass form Correspondence to: P.L. Parker, Marine Science Institute, The University of Texas at Austin, Port Aransas, TX 78373, USA. "Present address: Institute for Geophysics, The University of Texas at Austin, Austin, TX 78712, USA. vast submerged meadows in the Laguna Madre. The Laguna-Baffin Bay complex is a major producer of finfish on the Texas coast and the seagrass community is probably responsible for this important resource. This study was undertaken to gain insight into natural variations in seagrass productivity over the past few thousand years. Our interest centered on the isotopic record of seagrass-derived carbon preserved in sedimentary organic matter. Baffin Bay, an arm of the Laguna, is a drowned and partially filled Pleistocene river valley 37 km in length and 1.85-7.4 km wide. An earlier survey of the bay with a sonoprobe showed that the channels of the Pleistocene rivers are filled with up to 20 m of sediment in the bay centers (Behrens, 1963). The mouth 0168-9622/92/$05.00 © 1992 Elsevier Science Publishers B.V. All rights reserved. 224 B. ANDERSON ET AL. 2. Experimental PORT HOUSTON ~: i"k ~i!: - TEXAS GALVESTON BY ,~IU..E GULF OF MEXICO BA Y . ' ~CORPL tTI BAY ••:•~•::....... ¸¸•:: i:~:):!i:i BAFFIN BROWNSVILLE L [ ~ ~ BAY (LOWER)LAGUNA MADRE Fig. 1. Map of Texas coast showing Laguna Madre and Baffin Bay.Coring locations are × (core 2) and O (core 3). of the bay is partially silled by a fossil worm reef. Because the bay is hypersaline and somewhat oxygen depleted there is an almost total absence of a macro-infauna in the bay center, so that the sediments are largely undisturbed. Examination of short cores ( l0 cm) from the mouth of the bay showed that the fine-grained sediment contained from 1.0% to 2.5% organic matter, the ~3C of which ranged between - 18.5 and - 14.5%0 (Macko, 1981 ). Based on these data and Behren's (1963) sonoprobe survey it was felt that the 20-m section of sediment in Baffin Bay provides an exceptional opportunity for a geochemical and isotopic time-series study. An earlier core study provided a few ~4C dates which allowed an estimation of sedimentation rate (Behrens and Land, 1972). This paper reports on results from coring the upper part of the section and using stable isotope ratio variations to characterize the sources of organic matter in the sediments. The coring site was selected where the sediment was thickest (Fig. l ). Since the water depth in Baffin Bay is relatively shallow, ~ 2 m, a decision was made to construct a portable coring platform. Due to a relatively unobstructed long fetch of the winds the bay waters can be rough, making it quite difficult to use a small ship as a coring platform. The coring tower shown in Fig. 2 was built from recycled 3-in ( ~ 7.6 cm) oil-well drill pipe by the crew of the R / V "Longhorn" and was designed so that it could be transported by that ship. Once in place it provided a stabl¢ platform which allowed re-entry into the core hole and retrieval of multiple piston cores. Aluminum irrigation pipe (20 ft × 3 in or ~ 6.2 m × ~ 7.6 cm) was used as a core barrel. Handles, which clamped around the pipe, aided in inserting and removing the pipe. In general a crew of eight was able to take 5-m core sections. The core hole was L65 m Fig. 2. Portable coring tower. STABLE CARBON ISOTOPE VARIATIONS IN SEDIMENT FROM BAFFIN BAY, TEXAS kept open with AI pipe casing just slightly larger than the core barrel. Using this approach several cores of ~ 5 m length were taken. Two cores were taken at each of two sites in May and June of 1989. The sites were within 200 m of each other (Fig. l ). Three of the four cores reached a hard dolomite layer, one of several which were described by Behrens and Land (1972). They assigned it a 14C age of 2300 yr BP. Although more than half of the post-Pleistocene sediment lies below this marker no effort was made to core beyond it. Cores 2 and 3, one from each site, were used for the chemical and isotopic studies reported here. The fresh core was returned to the laboratory while still in the A1 core barrels. The core was extruded with the help of a hand-operated winch and the fresh sediment caught on A1 foil. The core was split using a large spatula which was maintained at 30 V d.c. relative to the AI core barrel and mud. The voltage was maintained by attaching one wire from a d.c. power supply to the spatula and one wire to the A1 foil onto which the core was extruded. The voltage repelled the wet clay from the blade so that a smooth core surface was obtained. The fresh cores, which showed clear laminations, were described and subsampled at 5- or 0.5-cm intervals for analysis. The subsamples were held in plastic bags in a deep freeze until processed. Sub-samples of the frozen samples were treated with 5% phosphoric acid to remove carbonates, the acid decanted through a glass fiber filter and the residue washed twice with distilled water. The sediment was collected on the filter, dried at 50°C and ground to a powder with a mortar and pestle. These samples were used for 613C and C, N analysis of total organic matter. A second sub-set of the frozen sample was processed for carbonate analysis. These samples were freeze-dried and reduced to a powder with mortar and pestle. Samples of the carbonate-free, dried sediment were weighed and combusted using the sealed tube method of Sofer (1980) to pro- 225 duce C O 2 suitable for isotopic analyses. Pyrex ® tubes containing the sediment and copper oxide were heated at 590°C for 3 hr and allowed to cool overnight. The volume of CO2 produced was measured man®metrically and the % TOC (total organic carbon ) calculated. The CO2 was then set aside for mass spectrometry. The CO2 from the carbonate containing sample sub-set was recovered by reacting a weighed subsample with 85% phosphoric acid for 1 hr. The sediments were rich in carbonate so that quantitative manometer readings were made to permit a calculation of percent carbonate. All C O 2 samples were analyzed on a VG ® 602E isotope ratio mass spectrometer using the correction procedures of Craig (1957). A laboratory standard of vacuum pump oil (AER ® ) was combusted to produce a working CO2 standard. The AER ® oil was calibrated relative to the Chicago PDB standard by comparing it to NBS 22 (Northam et al., 1981 ). The 6~3C of NBS 22 is taken to be -29%o vs. PDB; AER ® is - 27.32%o. The working standard for carbonate is the Woods Run Travertine, having a 613C of --9.17%o. All data are reported relative to the PDB standard. Carbon to nitrogen ratios were measured on the acidified samples using a Perkin-Elmer ® model 240 Elemental Analyzer. Although some organic matter is lost in the acidification process as soluble material, it is unlikely that the C / N ratio is significantly altered. 3. Results and discussion The concentration of total organic carbon, TOC, in the 5-m cores varies between 1% and 6% on a carbonate-free basis (Figs. 3 and 4; Table 1 ). A few samples composed of sand approached zero while a few which contained plant remains exceeded 7%. The small-scale variations seen in both cores are real. The TOC content is distinctly hig~er below the 4-m level in both cores. For comparison 33 surface sediment samples from nearby Corpus Christi Bay varied between 0.1% and 2.0%. The higher 226 B. ANDERSON ET AL. -50-50 150-150 + ..l CA 250 -250 _e "I@ CA 350- o -350 a~ G) (2 450-450 -550 -550 11'lIII' l,,,~I,r- I J I i ]--~FSTi,l,, 0 5 -16 % Organic Carbon -15 -14 -13 Del !3-C i, 10 15 CIN Atom Ratio Fig. 3. The variations with depth in core 2 of total organic matter (TOC) on a carbonate-free basis, J ' 3C of TOC, and the carbon to nitrogen ratio of organic matter. No data was obtained between 340 and 390 cm due to coring problems. The sample intervals were 5 cm. values for Baffin Bay may reflect better preservation due to a restricted water circulation, caused by the sill, which lowers oxygen and increases salinity. The C/N values generally range between 10 and 14 and like TOC cycle with depth (Figs. 3 and 4; Table 1 ). There is a gradual drift toward higher C / N ratios with depth. Fresh phytoplankton typically have C/ N ratios ~5.5-7.8 (Biggs et al., 1983; Hedges et al., 1988). Fresh seagrasses, on the other hand, are rather low in nitrogen, with C / N ratios near 20 (Farfan and Alvarez-Borrego, 1983). Assuming that C/N does not significantly change with diagenesis, the pattern of the C/N ratios is consistent with a model wherein the TOC is composed of mixtures of phytoplankton and seagrass. If so, then the relative l' 0 5 -16 % Organic Carbon l i I' I' -15 -14 -13 De113-C I~I'~I' 10 15 CIN Atom Ratio Fig. 4. The variations with depth in core 3 of total organic carbon (TOC) on a carbonate-free basis, ~'3C of TOC, and the carbon to nitrogen ratio of organic matter. The sample intervals were 5 cm. amount of plankton and seagrass must change on a time scale of decades based on the 14Cdata of Behrens and Land (1972). Such a change would reflect strong environmental changes such as salinity or temperature. The j~3C vs. depth curves (Figs. 3 and 4) show two general trends, the cyclicity seen in the TOC curves, and an overall shift to more positive J'3C-values with depth. In core 3 the upper section was lost so this shift is not seen, but it is present in the other three cores. The jl3C cyclicity, covering 4%0 in 4 m, is remarkable for an environment which at first glance seems to be constant. By contrast Gulf of Mexico cores of Pleistocene sediment showed 12%0 variations over 8 m of sediment (Newman et al., 1973). The analytical error associated with these data was evaluated in two ways. Repeated analyses of sub-sets of sediment STABLECARBONISOTOPE VARIATIONSIN SEDIMENT FROM BAFFINBAY,TEXAS 227 TABLE 1 TABLE 1 (continuea) Baffin Bay: cores 2 and 3 Depth (cm) Core 2 Depth Core 2 C/N Core 3 Core 3 %C C/N 15 20 24 30 35 40 45 50 55 60 65 70 75 80 85 90 96 100 105 110 115 120 125 130 135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 215 220 225 230 235 250 245 250 255 260 J'3C C/N %C (%o) (cm) 11.05 10.88 10.82 10.57 10.48 17.59 10.93 11.29 11.56 11.92 11.67 12.56 11.49 11.32 11.24 12.02 10.70 11.44 11.82 11.07 12.46 12.35 11.58 12.39 11.55 11.75 12.44 12.30 11.60 12.20 11.88 20.01 12.09 12.88 12.75 12.17 11.92 11.65 11.85 12.41 12.62 12.58 13.00 12.14 12.30 12.98 13.57 13.73 13.44 12.80 %C 2.52 2.35 3.56 2.70 2.64 3.43 2.42 3.77 3.14 4.03 2.28 4.21 2.58 2.60 2.30 3.58 2.72 2.35 3.28 2.76 3.46 4.31 3.14 3.19 2.03 1.95 4.08 3.97 2.53 1.37 2.10 2.12 1.86 2.00 1.38 0.12 2.78 3.08 3.05 3.11 2.58 3.49 2.46 1.95 2.08 3.68 3.25 3.95 3.64 3.36 c~13C C/N %C jl3C (%o) jI3C (%0) (%0) - 1 4 . 4 3 lostcore -15.34 - 14.73 -15.97 - 15.93 -15.81 - 1 4 . 8 4 10.57 3.96 - 1 4 . 7 6 10.35 3.63 - 1 5 . 3 8 13.92 3.66 -14.31 10.23 2.45 - 1 6 . 5 3 10.50 4.08 - 15.19 11.02 3.85 - 1 6 . 5 2 12.39 3.82 - 1 5 . 8 8 11.60 3.62 -15.99 9.50 2.81 - 1 6 . 0 5 11.66 2.86 - 1 4 . 5 6 10.45 2.79 - 1 5 . 5 3 11.56 2.71 -i;.19 14.37 2.19 - 1 4 . 5 2 11.1" 2.50 - 1 5 . 6 4 10.38 3.04 - 14.47 9.09 1.58 - 1 5 . 2 5 11.79 4.01 - 1 5 . 0 6 12.08 3.07 - 1 6 . 4 6 11.64 2.91 - 1 5 . 8 2 10.19 3.61 - 1 5 . 3 0 11.97 1.66 - 14.96 12.95 2.19 - 1 5 . 7 8 13.03 3.36 - 1 7 . 3 4 13.21 3.74 - 17.46 8.55 1.13 -16.01 13.27 2.64 -15.91 13.21 2.73 - 1 5 . 6 6 13.71 2.50 - 1 6 . 2 6 13.45 3.61 - 1 6 . 8 4 13.11 2.72 - 1 4 . 9 5 12.36 2.67 -14.61 12.24 2.39 - 15.60 13.12 3.37 -15.31 12.82 3.12 - 15.58 12.89 3.05 - 1 4 . 6 3 13.36 3.85 - 14.84 13.18 2.07 - 1 5 . 8 5 12.54 1.66 - 1 5 . 8 7 12.10 1 . 7 1 - 1 4 . 7 3 11.78 1.67 - 1 5 . 2 4 13.69 2.96 - 1 4 . 4 2 13.43 2.34 - 1 4 . 7 5 13.34 3.63 -15.61 12.84 2.81 - 13.61 -14.97 -14.44 -14.90 -13.85 - 13.85 - 14.61 -14.68 -15.09 -15.06 -14.26 -14.53 -15.18 -13.76 -14.86 -14.89 -15.22 -15.59 -14.60 -15.88 -16.58 -16.30 -15.26 -15.74 -16.26 -16.61 -16.16 -16.76 -15.41 -17.00 -15.67 -15.74 - 15.40 -14.92 -15.56 -15.57 -15.02 -15.38 -15.79 -15.93 -14.32 -14.64 -14.93 -15.33 265 270 275 280 285 290 295 300 305 310 314 315 320 323 325 326 330 335 340 345 350 355 360 365 370 374 378 380 385 390 395 400 405 410 415 420 425 430 435 440 445 450 455 460 461 465 470 475 480 485 490 495 12.79 13.11 12.88 12.78 12.71 13.35 13.71 12.93 13.15 12.99 13.57 12.41 12.14 2.54 3.03 2.54 2.00 2.09 3.59 4.44 3.03 3.15 3.67 4.15 3.84 4.31 -15.24 -13.97 - 14.80 - 14.94 - 15.29 - 14.77 -13.74 -15.45 -15.14 -14.71 - 14.62 - 14.60 -14.05 12.06 2.52 - 14.93 18.02 2.48 11.39 3.65 12.17 2.88 incomplete core -15.56 -15.90 -15.30 section 12.74 13.10 13.02 12.83 13.60 14.04 13.10 13.85 13.70 13.26 13.53 11.22 3.35 2.85 2.26 1.55 4.94 4.79 3.60 4.58 4.32 3.35 3.36 0.17 -15.10 -15.24 - 15.41 -16.04 -13.19 - 14.40 -14.51 -14.85 -14.86 -15.97 -15.33 -13.53 13.33 14.29 14.20 14.41 14.54 13.25 12.90 13.27 3.45 3.77 3.74 4.69 5.80 4.97 4.72 4.87 - 14.13 -14.52 -14.56 -13.85 - 13.10 - 13.59 - 15.14 - 13.78 13.03 11.99 11.98 13.44 12.53 13.10 12.47 12.76 12.79 12.84 2.76 1.53 2.07 3.66 2.30 4.60 3.37 4.21 3.29 3.91 --15.61 -15.05 -14.56 -12.78 -14.71 - 14.79 -15.26 -15.67 -14.85 - 14.41 12.51 12.39 12.38 3.65 2.89 2.92 -13.79 - 15.02 - 14.91 12.18 11.25 11.42 13.08 12.83 12.97 12.91 13.35 11.72 12.59 13.46 12.96 11.29 10.67 11.50 15.42 12.63 13.68 13.27 13.79 13.47 12.32 13.45 15.04 13.42 13.37 13.63 13.21 13.02 2.91 1.88 1.75 2.85 2.95 4.15 3.65 3.44 1.72 2.85 3.99 3.22 1.70 1.50 2.02 2.70 0.69 3.40 4.03 5.75 4.70 3.28 5.02 4.08 3.16 4.89 6.93 7.23 4.24 - 14.59 -15.02 -15.35 -13.90 - 15.06 - 13.21 - 14.90 - 15.12 - 15.92 - 15.22 - 15.01 - 14.06 -15.15 - 15.59 -14.57 - 15.92 -16.72 -14.32 - 14.51 -14.51 -14.81 -15.56 -15.71 -15.17 -14.40 -14.33 -14.29 -12.96 - 12.82 13.32 12.70 13.30 14.14 14.05 4.71 4.09 0.70 5.58 7.34 -15.03 -15.67 -14.87 -14.68 -15.18 228 B. ANDERSON ET AL. TABLE 1 (continued) Depth (cm) Core 3 Core2 C/N %C ~13C C/N %C disC (~) 500 505 510 515A* 515B* 520 525 530 535 540 12.19 11.87 12.74 5.91 12.56 14.25 13.07 13.77 13.64 12.65 4.12 3.99 6.42 0.34 3.28 5.53 5.41 10.34 5.23 5.92 - 14.63 -15.15 - 14.62 -13.58 - 13.54 -14.38 - 13.20 -14.41 - 14.74 -14.13 (~) incomplete core The sample depths are distance (cm) below the water-sediment interface; carbon to nitrogen ratios are atomic ratios; percent total organic carbon (TOC) is on a carbonate-free basis; J' 3C-values are relative to the PDB standard. *Core 2 contained thin, well-resolved layers of mud and sand at ~ 515-cm depth. Sample 515A is sand and 515B is mud. Dolomite rock was also present at 515 cm, but was not sampled here. samples gave a reproducibility of +_0.1%0 over a short time (days) and +_0,2%0 over a long time (weeks). The difference is due to the repeated preparation of standard CO2. In a second control experiment, subsamples were taken for which the entire procedure, beginning with subsampling the core, was repeated. Each of these was acidified, dried and burned separately. Excluding a sand sample with low TOC, the average standard deviation was +_0.3%0 for all samples and +_0.15%o for samples analyzed with the same working standard. Based on these data it seems safe to consider absolute variations of +_0.5%0 as real although trends are probably real to +_0.2%0 (B.R. Anderson, 1990). The cyclic variations are real within +_0.2%o based on the control experiments discussed earlier. This extra care to establish a reasonable level of confidence in the ~ 3 C data was necessary in order to insure that the sharp variations in ~ a c with depth are not experimental or sampling artifacts. In order to evaluate the influence of sample spacing on the pattern seen in Figs. 3 and 4 a set of subsamples was taken from core 3 using 0.5-cm intervals rather than the usual 5-cm ones. The results show considerable fine structure for ~3C enriched and depleted sections of the core (Fig. 5; Table 2). While the 0.5-cm data are the most interesting it appears that the 5-cm samples do not mask the major cycles and trends. Using Behrens' (1963) estimate of a sedimentation rate of 0.8 c m / l 0 yr, the series of values in Table 3 from 187 to 191.5 cm with ~aG-values of - 16.85+_0.06%o represent a 50-yr period of deposition with a fairly constant source of organic matter. On the other hand, the peak at 280 cm with a t~ac of 12.800 reflects a strong shift to a new ratio of source materials in ~ 1000 yr. The cyclic pattern of ~aC-values suggests that events of ~ 10-20-yr duration are resolved in the data. This is consistent with the historical frequency - -15.41 A. 190 -15.67 20O •I $,40 -17 -16 -15 -14 lJJllJl -16 I 260 -15 -14 Del 13-C -13 ~1[ -1533 Q 2zo 280 290 Fig. 5. A comparison o f ~ 3 C of TOC for core 3 using 5.0and 0.5-cm sampling intervals. The 5.0-cm data points are not plotted to the 0.5-cm t~3C scale, but are shown numerically. STABLE CARBON ISOTOPE VARIATIONS IN SEDIMENT FROM BAFFIN BAY,TEXAS TABLE 2 Baffin TABLE 2 Bay: core 3 229 (continued) %C Depth t~' 3C (cm) Depth %C (cm) 181 181.5 182 182.5 183 183.5 184 184.5 185 185.5 186 186.5 186.5 186.5 187 187.5 188 188.5 189 189.5 190 190.5 191 191.5 192 192.5 193 193.5 194 194.5 195 195.5 196 196.5 197 197.5 198 199 199.5 200 200.5 201 201 201.5 202 203 203.5 204 262 263 264 264.5 265 2.86 2.75 2.68 2.18 2.48 1.84 2.87 3,28 3.38 3.74 3,78 2,56 2.82 2.11 1.57 2.93 3.40 3.32 3.35 2.69 2.84 3.21 3.22 3.09 2.58 3.33 2.62 2.40 3.44 3.42 3.20 3.87 3.15 4.15 4.52 3.82 4.19 3.82 3.71 3.52 3.17 3.50 3.44 3.46 3.44 3.34 3.05 1.40 2.55 2.54 2.40 2.54 t~ ~3C (%o) 16.80 16.80 - 16.75 - 16.98 - 16.60 - 17.23 -16.18 -15.91 - 15.35 -15.17 - 15.34 - 15.87 - 15.90 - - 16.84 16.67 16.90 16.77 16.90 16.93 - 16.86 -16.88 -16.81 -16.89 -16.75 - 16.62 - 16.54 - 16.43 - 16.02 - 15.62 -15.15 -16.13 - 15.90 -16.12 -16.15 - 16.48 - 16.84 - 16.87 - 16.84 -16.70 - 16.93 - 16.95 - 16.98 - 16.88 - 16.82 - 16.89 -16.91 - 16.98 - 15.50 - 15.39 - 15.83 -16.11 - 16.25 - - (%o) 265.5 266 266.5 267 267.5 268 268.5 269 269.5 270 270.5 271 271.5 272 272.5 273 273.5 274 274.5 275 275.5 276 276.5 277 250.5 278 278.5 279 279.5 280 280.5 281 281.5 282 282.5 282.5 283 283 283.5 285.5 t~13Co f 2.91 1.96 2.70 2.65 2.55 2.06 1.46 2.33 2.21 2.06 2.99 2.55 2.53 2.30 2.18 2.68 2.78 3.00 2.85 2.61 2.21 2.10 2.00 1.87 1.94 1.98 2.39 3.86 4.33 4.28 3.35 2.53 3.49 2.63 1.82 1.66 2.15 2.16 2.90 3.03 total organic in sediment using -15.95 - 14.62 - 15.13 - 15.00 - 15.22 - 14.91 - 14.60 - 14.75 - 14.76 - 14.80 - 14.80 - 14.95 - 15.00 - 14.95 -15.19 - i 5.30 - 15.24 - 14.74 - 14.66 - 14.51 - 14.52 - 14.72 - 15.17 - 14.09 - 15.16 - 15.03 - 14.09 - 12.94 - 12.86 - 12.81 - 13.92 - 14.36 - 14.94 - 15.14 - 15.08 - 15.09 - 14.94 - 14.86 - 14.60 --14.50 matter 0.5-cm relative sample to PDB and percent TOC spacing. of droughts and hurricanes on the Texas coast. Jasper and Gagosian (1990) reported variations in t~3C and C / N for a 208.7-m core from the northern Gulf of Mexico. They explained the variations as being the result of mixing of two end-members, terrigenous and marine organic matter. This resembles the present stuay except that our end members are 230 B. ANDERSON ET AL. (continued) TABLE 3 TABLE 3 Baffin Bay: core 3 Depth (cm) %C J t 3C (%0) 355 360 365 370 374 378 380 385 390 395 400 405 410 415 420 430 435 440 445 450 455 460 465 470 475 480 485 495 0.86 1.27 0.17 1.70 1.24 1.22 0.48 0.63 1.08 1.02 1.24 1.25 1.11 1.14 1.64 1.18 2.01 0.97 0.92 1.05 0.87 0.88 0.89 8.04 -0.24 -0.81 -0.47 -0.87 + 1.22 -0.30 -2.67 -0.22 - 1.09 - 1.01 - 1.24 - 1.74 - 1.36 -2.06 -0.96 - 1.13 -0.68 -0.71 - 1.48 - 1.58 - 1.96 - 1.29 -0.99 - 1.51 +2.92 Depth (cm) %C 50 55 60 65 70 80 85 90 95 100 105 I 15 120 125 130 135 140 145 150 160 170 175 180 185 190 195 200 205 210 220 225 230 240 245 250 255 260 265 270 275 280 285 290 295 300 305 320 323 326 330 335 345 350 1.35 1.31 1.44 1.55 1.07 0.37 0.66 0.83 0.50 0.45 0.44 0.97 1.05 0.89 0.21 0.93 0.72 0.35 0.99 0.74 0.30 0.30 0.53 1.07 0.29 0.55 I. ! 5 i.04 0.20 0.64 I. l I 1.96 1.40 1.10 1.14 0.95 1.16 0.45 0.45 1.32 2.24 j ~3 (%0) + 0.83 +0.19 + 0.68 - 0.19 + 0.41 - 0.90 - 1.81 - 0.64 - 2.00 - 0.02 - 0.79 - 1.41 - 0.44 -0.81 - 2.54 -0.58 - 0.68 -0.13 - 1.55 - 0.41 - 0.03 + 0.60 - 0.03 + 0.64 - 0.31 - !.26 - 1.39 - 1.00 -0.18 - 2.28 - 0.71 + 0.04 - 2.24 - 0.97 - 1.04 - 0.64 - l.O0 - 1.09 + 0.24 + 0.25 +0.58 +0.58 - 1.02 -2.11 - 1.82 -2.89 -0.91 -0.58 -2.20 -0.97 - 1.33 - 1.45 +0.35 T h e precent o f carbonate carbon a n d •13C o f carbonate carb o n relative to PDB; the d e p t h intervals ( c m ) are the distance b e l o w the seawater s e d i m e n t interface. plankton and seagrass. However, the time frame is very- different, 2000 vs. 100,000 yr. For this reason their sampling frequency did not show the fine-scale variations seen in Baffin Bay. Nevertheless, it is interesting that mixing processes are preserved in two such different environments and time spans. Behrens and Land (1972) reported jlaCvalues for carbonates in the Baffin Bay cores from - 3 . 0 to + 4.2%o. The carbonate sample in core 3 at 495 cm (Table 3) with a jI3C of + 2.92%0 is probably the dolomite layer that Behrens and Land (1972) encountered. In their core two dolomite layers only 1 cm apart had jl3C-values of + 1.9 and ~-4.2°/o0. They conclude that the dolomite is marine in origin and probably is the result of direct precipita- STABLECARBON ISOTOPE VARIATIONSIN SEDIMENT FROM BAFFIN BAY,TEXAS tion. They suggested that the more 13C-depleted samples might be the result of organicderived CO2. Because the sediment was rich and variable in TOC we expected to observe some rather negative carbonates. For core 3 the t~3C-values fell between - 3 and + 1%o except for two more positive samples (Fig. 6). The slight dominance of negative values may be the result of post-depositional oxidation of organic matter. Such a process is not a major pathway for carbon in this system as compared to fine-grained carbonates from Gulf of Mexico cores wherein values as light as -22.7%o were reported (R.K. Anderson et al., 1983). The absence of a trend toward more negative values with depth indicates that over the 2000 yr represented by core 3, bacterial remineralization of the TOC has been minimal. We suggest that a simple model which con- g, , ~ T -350 g -450 -550 ' 0 I 1 ' ~ ' 2 ' I ' I -1 0 Weight Percent ' ( ' 1 I 2 ' I 3 De113-C Fig. 6. The percent carbonate carbon and ~3C of total carbonate for core 3. 231 siders two sources of organic matter can explain the variations in the isotopic and elemental data in these sediment cores. In the model, Baffin Bay TOC is a mixture of material derived from seagrass and phytoplankton, the two major plant types in the system. Changes in the relative amounts of these two sources can account for the cyclic patterns and the long term drift of t~13C of TOC. The extensive seagrass meadows of the Laguna Madre provide a source of organic matter which is 13C rich (t~ ~3C~, - 10%o) (Parker, 1964). Baffin Bay is too deep for seagrass growth except along bay edges. However, the bay supports a phytoplankton community which is highly productive. During the course of this study we attempted to obtain pure phytoplankton from the bay by size fractionation with only limited success. By luck, in the summer of 1990, the whole Laguna Madre system including Baffin Bay was subject to a massive phytoplankton bloom. The bloom persists to this time, May 1991. The standing crop was so high that a 99% pure culture could be obtained by simply filtering 1 I of the brown water. The blooming organism has not been fully identified, but it is a small, golden Chrysophyte. The t~]aC-value of the bloom is -20.3_+2.0%0. The cause of the bloom is not known but it may be associated with a series of cold winters which caused a fish kill. Fortunately, the organism has not proved to be toxic; however, the bloom is so intense that there is concern that it may impact the seagrass beds by depriving them of light. It is this kind of environmental stress favoring one plant type or the other which could cause the variations seen in these cores. If one uses these two end members, seagrass ( - 10%o)and phytoplankton ( - 20%o) then it is understandable that all of the data points in Figs. 3 and 4 fall between these values. A value of - 150/00for TOC would correspond to a 50:50 mixture of seagrass and phytoplankton. There is no doubt that a strong seagrass signal is seen in several sections of the core. 232 Changes in source TOC such as those which affect a whole bay and persist for tens to hundreds of years must reflect substantial changes in the local environment. At the present time the J~ac of sediment TOC can be seen to reflect a decreasing seagrass signal as one moves from grass meadows toward the open, plankton dominated, Corpus Christi Bay (Fry et al., 1977). Phytoplankton grow under most conditions of salinity and temperature, depending mostly to the availability of light and nutrients. Thus phytoplankton input can be considered to be fairly constant, but subject to intense blooms such as was seen in the 1990 bloom. Seagrasses on the other hand grow best at seawater salinities. They are doing well in the hypersaline lagoon now. However, prior to the dredging of the Intracoastal Canal in 1948, local commercial fishermen maintain that little seagrass grew in the Laguna Madre because it was too saline. Breuer (1957) argues that as recently as 1850 Baffin Bay enjoyed a sustained period of lower salinity, citing evidence of oyster collection in the Bay by the native Karankawa Indians. If so it would have been a period of flourishing seagrasses. Large hurricanes breach the barrier island, Padre Island, forming passes which can stay open for years and which allow seawater to flow into the system thus preventing hypersalinity and stimulating seagrass productivity. Cyclic events such as hurricanes and massive plankton blooms can account for the shortterm cycles in the J~ac curves. The drift toward more seagrass-rich values deep in the core must reflect a more general change such as a long period of higher rainfall in the drainage basin. This would also freshen the Laguna and stimulate seagrass growth. We have no independent evidence for this but it is mentioned to identify topics worth further study. The picture described here is, no doubt, overly simple, but it is consistent with the J~ac, C / N and percent TOC patterns. Certainly modest land plant input is present but it may be isotopicaUy leutral in that the local grass- B. ANDERSON ET AL. lands are a mixture of plants which fix carbon by the C3 (j'3C~-26°/oo) and C4 (J~3C - 10°/oo) pathways (Fry and Sherr, 1984). Blue-green algae (j~3C~, - 13%o) may be important in periods of extreme salinity (Behrens and Frishman, 1971 ). There is no evidence in the sediment for substantial C3 plant input, unlike estuaries which border on highrainfall landscapes (Sackett and Thompson, 1963). 4. Conclusions Baffin Bay, Texas, sediments retain a record of the isotopic and chemical history of the region, which reflects local cyclic events and climate for the last 2000 yr and probably for the last 8000 yr. This study of the total organic matter of cores indicates that at least two major sources of organic matter have varied in their relative contribution to TOC: ( 1 ) J~aCToc-values cycle over 4%o in a 4-m interval of core (Figs. 3-5 ). This range is consistent with varying quantities of phytoplankton ( - 20%o) and seagrasses ( - 10%o) being the source of the TOC. No J~ac data was as negative as -25%0, which would indicate a terrestrial source, was found. (2) Total carbonate J~aG-values fell in a range of - 3 to + 1o/ooexcept for two more positive values. There was no trend toward more negative carbonate with depth (Fig. 6). This suggests that bacterial oxidation of TOC is not a dominant process in the time period the~e cores represent. It is certain that the small carbonate lenses seen in the core are not the result of intense oxidation of TOC but are inorganic precipitates. A final conclusion is that restricted coastal environments like Baffin Bay hold considerable geochemical information on past regional climate and weather variations which would be of interest. STABLE CARBON ISOTOPE VARIATIONS IN SEDIMENT FROM BAFFIN BAY, TEXAS Acknowledgements This work was supported by Grant No. 4541 from the Texas Higher Education Coordinating Board, Advanced Technology Program. We thank Capt. Don Gibson and the crew of the R/V "Longhorn" for constructing and transporting the coring tower and for their help with coring. We thank Dr. Dave Jeffries of Chevron Oil Co. for the Woods Run Travertine standard. References Anderson, B.R., 1990. Ecological implications of isotopic evidence for varying input of organic matter into sediments of Baffin Bay, Texas. Masters Thesis, The University of Texas at Austin, Austin, Texas, I 12 pp. Anderson, R.K, Scalan, R.S., Parker, P.L. and Behrens, E.W., 1983. Seep oil and gas in Gulf of Mexico slope sediment. Science, 222:629-62 I. 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