The Black Sea, with its oxic, suboxic and anoxic layers, provides a unique environment for studying how biological and geochemical processes affect the composition of particulate matter. The elemental composition of particles in the Black Sea is controlled by their origin and sources. Particles from rivers are dominated by aluminosilicate material that has compositions similar to the earth&rsquo / s crust. In general this material is relatively unreactive. Biological processes in the upper oxic and suboxic layers of the water column result in enrichments of elements which used as nutrients. Cu, Ba and Mo have been proposed as tracers for planktonic material and new production. Geochemical processes like manganese and iron recycling between oxidized and reduced forms, metal sulfide formation, and biogenic matter decomposition can have a large impact on the composition of particles in the suboxic and anoxic zones.
The aim of this thesis was to study the composition of particles suspended in the water column of the Black Sea, in regional rivers draining into the Black Sea, and of particles deposited in these rivers and Black Sea sediments. The objectives were to determine the chemical composition and distribution of particles supplied by rivers and produced in the Black Sea, and compare with those particles buried in the sediments. The chemical distributions can help us to understand the biogeochemical processes taking place. The ultimate goal is to understand if there is a chemical signature that characterizes sediments deposited in anoxic basins that can be used to determine if ancient sedimentary rocks were deposited under such conditions.
Water column filter samples were collected from the central western basin and along transects to the SW shelf regions during several research cruises of R/V Bilim and R/V Knorr in the Black Sea. Samples were taken by using both in situ large volume filtration systems and on deck vacuum filtration of discrete samples. River samples were collected by hand from the bank of four Turkish rivers and the Danube River. Sediment samples were obtained from 0 - 25 cm interval of a box core from the deep western basin.
All samples were digested and analyzed by inductively coupled plasma - mass spectrometry and combination of atomic absorption (flame & / graphite furnace) instruments. The elements analyzed included Al, Ti, V, Cr, Mn, Fe, Ni, Co, Cu, Zn, Mo, Ag, Cd, Ba, Pb, and U. Great care was taken to avoid contamination and to obtain the highest level of precision and accuracy. The precision was typically about 5% for most elements. The accuracy, determined using standard reference materials, was also usually better than 5%. Another goal of this research was to determine the metal concentrations and best digestion methods using different types of filter materials. Blank filters were digested and analyzed and the analyses of various filter blanks are presented in the thesis.
The analyses showed that the particulate matter data from Turkish Rivers were very similar to the composition of global average riverine particulate material and global average crust. The Danube River had elevated concentrations for some elements that were probably due to anthropogenic contamination. The Turkish river samples were closer to (but still higher than) the averages for the world&rsquo / s rivers but many elements in the Danube were much higher. These high values determined for major elements in the Danube samples strongly suggest considerable contamination of the Danube as compared to the Turkish Rivers. The Danube River samples were especially enriched in Pb, Zn, Ag, Cu, Cd, and Mn and slightly enriched with Cr and Ni. The first five elements, in particular, are well known indicators of pollution.
The particulate matter in the water column of the Black Sea was influenced by lithogenic input from rivers, biological processes and geochemical processes. In order to examine the biogeochemical processes extensively, all the data were plotted as Metal/Al (Me/Al) ratios and compared with the ratios of the average crust and Turkish Rivers. Deviations were used to examine the anomalies due to biological and geochemical processes. In addition, the Al content of individual sample and the Me/Al ratio of crust or rivers were used to subtract the lithogenic component from the total composition. Enrichments due to biological processes were observed for Ba > / Fe > / Cr > / Mn > / Zn > / Ni > / Cu > / Mo > / V > / Co > / Cd > / U for the overall biogenic composition. Enrichments due to biology are most evident for Ba, Fe, Cr and Mn. This is a unique data set as there have been few previous analyses of biological enrichment for most of these elements.
The results of particulate matter analyses showed that some elements including U, V, Cr, Ni, Cu, Co, Zn, Ba and Mo were enriched in the set of samples from the euphotic zone. Redox cycling in the suboxic zone was observed, as expected, for Mn and Fe, whose oxides play an important role in scavenging processes. The redox dependent processes in the suboxic &ndash / anoxic interface influence the vertical distribution of U, Ni, Co, Cu, Zn, Ba and possibly Mo, Cr and V. Elements influenced by sulfide formation in the anoxic layer are Fe, Cr, Ni, Co, Mo, and presumably Ag.
The sediment data were also examined based on the same approaches. The elements Zn, Pb, U and Cd decreased with sediment depth over the top 5 cm suggesting that they were remobilized out of the sediments. In general the sediments from the Black Sea have Me/Al ratios very similar to local Turkish Rivers and average crust. There is no unique sediment signature (except possibly for Mo) indicating that these sediments were deposited under sulphidic conditions. This study does not support the hypothesis that the composition of ancient rocks can be used to characterize the environment of deposition.
| Identifer | oai:union.ndltd.org:METU/oai:etd.lib.metu.edu.tr:http://etd.lib.metu.edu.tr/upload/12606507/index.pdf |
| Date | 01 July 2005 |
| Creators | Yigiterhan, Oguz - |
| Contributors | Yemenicioglu, Semal - |
| Publisher | METU |
| Source Sets | Middle East Technical Univ. |
| Language | English |
| Detected Language | English |
| Type | Ph.D. Thesis |
| Format | text/pdf |
| Rights | To liberate the content for public access |
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