Pyrite formation under conditions approximating those in anoxic sediments: II. Influence of precursor iron minerals and organic matter

In the paper (Wang and Morse, 1996) that preceded this study, we presented results of experiments performed using a silica gel crystal growth technique to produce pyrite under conditions approximating those commonly occurring in anoxic marine sediments. The primary focus of that study was on the chemical pathways that pyrite formation follows and how differing conditions influenced reaction kinetics and morphology of pyrite crystals. In this paper, we present results of further long-term (up to 1 y) studies of pyrite formation, using the silica gel experimental technique, in which we investigated the role that different precursor iron (hydr)oxide minerals and marine organic matter play in pyrite formation. The minerals studied were akaganeite (β-FeOOH), ferrihydrite (Fe₅HO₈ · 4H₂O), goethite (α-FeOOH), hematite (α-Fe₂O₃), lepidocrocite (γ-FeOOH), and magnetite (Fe₃O₄). Marine organic matter used in this study was freeze-dried plankton collected from near-surface water in the Gulf of Mexico. The influence of precursor iron (hydr)oxide mineralogy, although important for initial iron sulfidization rates, was relatively minor compared to other variables, such as solution pH and sulfide concentration, in controlling the rate of pyrite formation. Consequently, major variations in the observed rate of pyritization of different iron (hydr)oxide minerals in sediments (e.g., Canfield and Berner, 1987) may reflect large differences in surface areas of the minerals rather than their intrinsic reactivity and is a confirmation of the estimates of Canfield et al. (1992) that most iron oxides have similar reactivity. The presence of marine organic matter (freeze-dried plankton) caused an increase in the sulfidization rate of goethite and a major (about 20 ×) decrease in the rate of pyrite formation. This can be interpreted as indicating that organic matter-iron interactions are important in both iron (hydr)oxide dissolution, and pyrite nucleation and growth. A possible explanation for this behavior is that dissolved organic matter produced during the long experiments (up to 1 year) increased the rate of goethite dissolution while inhibiting pyrite nucleation and growth by complexing iron. The lessons learned in the study of other mineral reaction kinetics (e.g., calcite and aragonite), that rates determined in pure inorganic systems, may not always be reliably applied to natural systems where organic matter can significantly influence mineral dissolution and growth rates, are, alas, repeated here for pyrite.     

Contrasting chemical and isotopic compositions of organic matter in Changjiang (Yangtze River) estuarine and East China Sea shelf sediments

To examine the source and preservation of organic matter in the shelf sediments of the East China Sea (ECS), we measured bulk C/N and isotopes, organic biomarkers (n-alkanes and fatty acids) and compound-specific (fatty acids) stable carbon isotope ratios in three sediment cores collected from two sites near the Changjiang Estuary and one in the ECS shelf. Contrasting chemical and isotopic compositions of organic matter were observed between the estuarine and shelf sediments. The concentrations of total n-alkanes and fatty acids in the shelf surface sediments (0–2 cm) were 5–10 times higher than those in estuarine surface sediments but they all decreased rapidly to comparable levels below the surface layer. The compositions of n-alkanes in the estuarine sediments were dominated by C₂₆-C₃₃ long-chain n-alkanes with a strong odd-to-even carbon number predominance. In contrast, the composition of n-alkanes in the shelf sediment was dominated by nC₁₅ to nC₂₂ compounds. Long-chain (>C₂₀) fatty acids (terrestrial biomarkers) accounted for a significantly higher fraction in the estuarine sediments compared to that in the shelf sediment, while short-chain (<C₂₀) saturated and unsaturated fatty acids were more abundant in the shelf surface sediments than in the estuarine sediments. Stable carbon isotopic ratios of individual fatty acids showed a general positive shift from estuarine to shelf sediments, consistent with the variations in bulk δ ¹³C_TOCTOC. These contrasts between the estuarine and shelf sediments indicate that terrestrial organic matter was mainly deposited within the Changjiang Estuary and inner shelf of ECS. Post-depositional diagenetic processes in the surface sediments rapidly altered the chemical compositions and control the preservation of organic matter in the region.     

A simple guideline to apply excitation-emission matrix spectroscopy (EEMs) for the characterization of dissolved organic matter (DOM) in anoxic marine sediments

Marine sediments represent a major carbon reservoir on Earth. Dissolved organic matter(DOM) in pore waters accumulates products and intermediates of carbon cycling in sediments. The application of excitation-emission matrix spectroscopy(EEMs) in the analysis of subseafloor DOM samples is largely unexplored due to the redoxsensitive matrix of anoxic pore water. Therefore, this study aims to investigate the interference caused by the matrix on EEMs and propose a guideline to prepare pore water sam...     

Optical properties of estuarine dissolved organic matter isolated using cross-flow ultrafiltration

Dissolved organic matter(DOM) from freshwater, mid-salinity, and seawater endmember samples in the Jiulong River Estuary, China were fractionated using cross-flow ultrafiltration with a 10-kDa membrane. The colloidal organic matter(COM; 10 kDa–0.22 μm) retentate, low molecular weight(LMW) DOM(10 kDa) permeate, and bulk samples were analyzed using absorption spectroscopy and three-dimensional fluorescence excitation-emission-matrix spectroscopy. The UV-visible spectra of COM were very similar to those obtained for permeate and bulk samples, decreasing monotonically with increasing wavelength. Most of the chromophoric DOM(CDOM, expressed as the absorption coefficient a355) occurred in the LMW fraction, while the percentage of CDOM in the colloidal fraction was substantially higher in the freshwater endmember(13.4% of the total) than in the seawater endmember(6.8%). The bulk CDOM showed a conservative mixing behavior in the estuary, while there was removal of the COM fraction and a concurrent addition of the permeate fraction in the mid-salinity sample, implying that part of the colloidal CDOM was transformed into LMW CDOM. Two humic-like components(C1: 250, 325/402 nm; and C2: 265, 360/458 nm) and one protein-like component(C3: 275/334 nm) were identified using parallel factor analysis. The contributions of the C1, C2, and C3 components of the COM fraction to the bulk sample were 2.5%–8.7%, 4.8%–12.6%, and 7.4%–14.7%, respectively, revealing that fluorescent DOM occurred mainly in the LMW fraction in the Jiulong River Estuary. The C1 and C2 components in the retentate and permeate samples showed conservative mixing behavior, but the intensity ratio of C2/C1 was higher in the retentate than in the permeate fractions for all salinity samples, showing that the humic component was more enriched in the COM than the fulvic component. The intensity ratio of C3/(C1+C2) was much higher in the retentate than in the permeate fraction for mid-salinity and seawater samples, revealing that the protein-like component was relatively more enriched in COM than the humic-like component. The contribution of the protein-like component(C3) to the total fluorescence in the retentate increased from 14% in the freshwater endmember to 72% for the seawater endmember samples, clearly indicating the variation of dominance by the humic-like component compared to the protein-like component during the estuarine mixing process of COM.     

Genesis of organic matter in the Kara Sea bottom sediments

Based on simultaneous use of organic and geochemical indicators (δ¹³C, C/N, and n-alkanes), the genesis of organic matter (OM) in recent bottom sediments of the Kara Sea was characterized. Maps for percentages and absolute masses of marine and terrigenous OM were drawn. The masses of buried marine and terrigenous OM were compared to its supply to the sea and onto the sea bottom.     

Partitioning of organic matter in continental margin sediments among density fractions

Hydrodynamic processes sort and redistribute organic matter (OM) and minerals on continental margins. Density fractionations were conducted on sediments from diverse margins (Mexico margin, Gulf of Mexico, Mississippi River delta, Eel River margin) to investigate the nature, provenance and age of OM among density fractions. Mass, elemental (C and N), lignin, and surface area distributions, as well as stable carbon and radiocarbon isotopic compositions were measured. The lowest density fractions (< 1.6 g cm^− 3) contained the highest organic carbon (OC) (up to 45%) and lignin concentrations (up to 8 mg g^− 1) due to abundant woody debris, whereas high density fractions (> 2.5 g cm^− 3) were OC-poor (%OC < 0.5) mineral material. Most sediment mass was found in the mesodensity fractions (1.6 to 2.5 g cm^− 3) that contained the highest proportion of OC (up to ~ 75%) for each sediment. Stable carbon isotope compositions (δ¹³C − 25.5‰ to − 22.9‰) show terrigenous OC as a significant component of density isolates from the river-dominated sediments (Gulf of Mexico, Mississippi River, and Eel margin), whereas the Mexico margin, least influenced by riverine input, was dominated by autochthonous marine OC (δ¹³C ~ − 21.5‰). Radiocarbon compositions of density fractions indicate significant pre-aged OC (Δ¹⁴C as low as − 900‰) in river-influenced sediments but not on the Mexico margin (Δ¹⁴C > − 200‰). Ratios of vanillic acid to vanillin (Ad/Al)v among lignin oxidation products increase with increasing particle density suggesting variable lignin sources or selective degradation of lignin among the different density fractions.     

The conservative and non-conservative behavior of chromophoric dissolved organic matter in Chinese estuarine waters

The spectral absorption properties of chromophoric dissolved organic matter (CDOM) and their distributions in two Chinese estuaries, the Yangtze River Estuary and the Jiulong River Estuary, were studied during August 2003 (wet season) and during different seasons between 2003−2005, respectively. The CDOM concentrations (a₃₅₅) of fresh end members in the Jiulong River Estuary varied seasonally, while its quality remained relatively stable. However, the a₃₅₅ of the marine end members exhibited less variability. Application of a conservative mixing model indicated that CDOM behaved conservatively in the Yangtze River Estuary. No photobleaching removal was observed at high salinity region of this estuary. Although CDOM showed conservative behavior for many cruises in the Jiulong River Estuary, there was evidence for removal in the low salinity regions during some cruises. Laboratory mixing experiments and a salt addition experiment suggested that particle sorption of CDOM maybe the possible reason for the removal. These results showed that absorption properties of CDOM can be used as a tool to observe the quantitative and qualitative dynamics of DOM during estuarine mixing.     

The role of organic matter in the sorption capacity of marine sediments

Past studies have suggested that desiccation enhances hydrophobicity of salt marsh sediment, and that drying and rewetting sediment can be used to investigate sorption mechanisms of amino acids and other organic compounds [Liu, Z., Lee, C., 2006. Drying effects on sorption capacity of coastal sediment: The importance of architecture and polarity of organic matter. Geochim. Cosmochim. Acta 70, 3313–3324]. Here we further develop this technique to study sorption of hydrophobic and hydrophilic organic compounds in a wide range of marine sediments. Our results show that hydrophilic compounds sorb strongly to wet coastal sediments; in dried sediments, sorption of hydrophilic compounds decreases, while sorption of hydrophobic compounds is greatly enhanced. Small compounds with aromatic rings sorb more in dried than wet coastal sediments, suggesting that aromatic groups have a stronger effect on sorption than polar groups like amino and carboxyl moieties. Sorption of lysine, glutamic acid and putrescine decreases greatly when sediment is pretreated with KCl, indicating the importance of cation ion exchange. However, α-amino acids sorb much more than corresponding β- or γ-amino acids, and l-alanine sorbs more than d-alanine, suggesting that amino group location and chiral selectivity play an important role in sorption. Comparison of lysine and tyrosine sorption in different sediments indicates that source and diagenetic state of organic matter are important factors determining sorption capacity. Lysine sorbs much more to organic detritus from salt marsh sediment than to fresh Spartina root materials, marine particles, lignin or humic acids, indicating the importance of structural integrity in sorption. Desorption hysteresis of glutamic acid, putrescine and lysine (in dried sediment) suggests the presence of enzyme-type sorption sites of high sorption energy or multiple binding mechanisms. Taken together, these findings suggest that organic matter plays the major role in amino acid sorption in organic-rich sediments.     

Release of dissolved organic matter during oxic and anoxic decomposition of salt marsh cordgrass

Chromophoric dissolved organic matter (CDOM), as the light absorbing fraction of bulk dissolved organic matter (DOM), plays a number of important roles in the global and local biogeochemical cycling of dissolved organic carbon (DOC) and in controlling the optical properties of estuarine and coastal waters. Intertidal areas such as salt marshes can contribute significant amounts of the CDOM that is exported to the ocean, but the processes controlling this CDOM source are not well understood. In this study, we investigate the production of DOM and CDOM from the decomposition of two salt marsh cordgrasses, Spartina patens, a C₄ grass, and Typha latifolia, a C₃ grass, in well-controlled laboratory experiments. During the seven-week incubation period of the salt marsh grasses in oxic and anoxic seawater, changes in dissolved organic carbon (DOC) concentrations, dissolved nitrogen (DN) concentrations, stable carbon isotopic composition of DOC (DOC-δ¹³C), and CDOM fluorescence demonstrate a significant contribution of DOC and CDOM to estuarine waters from salt marsh plants, such as Spartina and Typha species. In the natural environment, however, the release processes of CDOM from different cordgrass species could be controlled largely by the in situ oxic and anoxic conditions present during degradation which affects both the production and decomposition of DOC and CDOM, as well as the optical properties of CDOM in estuarine and coastal waters.     

Geochemistry of organic matter in bottom sediments of the Ashadze hydrothermal field

Comparative studies of the composition and distribution of the dispersed organic matter (DOM) were performed for the bottom sediments from active areas of the Ashadze hydrothermal field (the Mid-Atlantic Ridge, 13° N) and for background sediments from the area treated (sampled during the cruises of R/V Professor Logachev in 2003 and 2007). The content of hydrocarbons (HCs) in the hydrothermal samples is about 20 times as high as the background values. The HCs composition includes both low-transformed (isoprenoids, hopenes, ββ-hopanes, and ααα27R-steranes) and geologically mature chemofossils (C₁₆-C₃₅ n-alkanes, geohopanes, moretanes, and polyaromatic hydrocarbons). The polyaromatic hydrocarbons (PAHs) are mainly represented by phenanthrene and its alkyl homologues, i.e., by possible products of the diagenetic transformation of biogenic precursors. The results obtained point to the mixed genesis of the hydrothermal DOM, which is caused first by the diversity of the biota composition in the considered region, as well as by the specificity of the processes of the DOM’s maturing under the extreme environmental conditions.     

Chromatographic studies of dissolved organic matter and copper-organic complexes isolated from estuarine waters

Dissolved organic matter (DOM) and dissolved copper-organic complexes were isolated from the estuarine waters of Narragansett Bay, RI, using reverse-phase liquid chromatography (RPLC). Different types of reverse-phase BOND ELUT columns (Analytichem International), including C₂, C₁₈ and phenyl-bonded phases, were studied to determine their adsorption efficiency for extracting DOM. Extraction efficiencies followed the order phenyl > C₁₈ > C₂, and phenyl − C₁₈ > C₂ for DOM and organic copper, respectively. However, comparisons of BOND ELUT and C₁₈ SEP-PAK (Waters Associates) columns indicated that SEP-PAK columns were the most efficient when both DOM and organic copper were considered. Chromatographic profiles of the isolated DOM obtained using high-performance liquid chromatography were similar in elution characteristics and resembled chromatograms typical of fulvic acid. The UV-absorption characteristics of the DOM showed small differences and suggested that the different reverse-phase columns isolated material that was qualitatively similar.Copper-organic complexes isolated using C₁₈ RPLC were studied to examine the dissociation of organically bound copper in seawater as the pH is lowered. Only a small amount of the complexed copper was displaced by the H⁺ with about 40% of the copper remaining bound at pH 3. However, the chromatographic elution behavior of the DOM and organic copper was significantly altered under acidic conditions as a result of protonation of acidic functional sites on the organic matter.     

Fluorescence characteristics of organic matter released from coastal sediments during resuspension

Excitation–emission matrix (EEM) fluorescence spectroscopy was employed to study the chemical nature of organic matter readily released into solution from sediment particles during episodes of resuspension. Surface sediment samples collected from five locations within the Hudson River Estuary and the Inner New York Bight were resuspended in their respective bottom waters for periods ranging from 30 s to 2 h. In most cases, fluorescence characteristics of the sample after resuspension differed from those predicted by conservative mixing of bottom and pore waters. Examination of excitation–emission matrices revealed that resuspension resulted in: (1) more intense humic-like fluorescence (Ex/Em 310/420 nm), and (2) greater fluorescence in the longer wavelength region of the spectrum (Ex/Em 330–388/440–480 nm) relative to the predicted values. Trends in the positions of excitation–emission maxima reported in the literature strongly suggest that fluorophores emitting at longer wavelengths are associated with increasingly degraded and/or aged organic matter. Thus, the data imply that resuspension of estuarine and coastal marine surface sediments releases degraded and/or aged, mineral-bound organic matter from the sediment matrix to the surrounding bottom waters.     

Nitrogen and carbon isotopic composition of marine and terrestrial organic matter in Arctic Ocean sediments:: implications for nutrient utilization and organic matter composition

Relationships between organic carbon, total nitrogen and organic nitrogen concentrations and variations in δ¹³C_org and δ¹⁵N_org are examined in surface sediments from the eastern central Arctic Ocean and the Yermak Plateau. Removing the organic matter from samples with KOBr/KOH and determining residual as well as total N shows that there is a significant amount of bound inorganic N in the samples, which causes TOC/N_total ratios to be low (4–10 depending on the organic content). TOC/N_org ratios are significantly higher (8–16). This correction of organic TOC/N ratios for the presence of soil-derived bound ammonium is especially important in samples with high illite concentrations, the clay mineral mainly responsible for ammonium adsorption. The isotopic composition of the organic N fraction was estimated by determining the isotopic composition of the total and inorganic nitrogen fractions and assuming mass-balance. A strong correlation between δ¹⁵N_org values of the sediments and the nitrate concentration of surface waters indicates different relative nitrate utilization rates of the phytoplankton in various regions of the Arctic Ocean. On the Yermak Plateau, low δ¹⁵N_org values correspond to high nitrate concentrations, whereas in the central Arctic Ocean high δ¹⁵N_org values are found beneath low nitrate waters. Sediment δ¹³C_org values are close to −23.0‰ in the Yermak Plateau region and approximately −21.4‰ in the central Arctic Ocean. Particulate organic matter collected from meltwater ponds and ice-cores are relatively enriched in ¹³C (δ¹³C_org=−15.3 to −20.6‰) most likely due to low CO₂(aq) concentrations in these environments. A maximum terrestrial contribution of 30% of the organic matter to sediments in the central Arctic Ocean is derived, based on the carbon isotope data and various assumptions about the isotopic composition of the potential endmembers.     

Estuarine transformation of organic matter: single coalescence events of estuarine surface active particles

Individual surface-active particles (SAP) in aqueous environmental samples can be characterized through their coalescence at a model hydrophobic interface. Each coalescence event is recorded as an electrical signal. As the electrical signal is a current transient (time on a millisecond scale), the sequence of fast processes leading to the formation of a condensed film can be studied from the moment of first attachment at the interface.In the stratified Krka Estuary, SAP are present in maximum concentrations (10⁷−5 × 10⁸ particles l⁻¹ min the size range > 1 μm) at the halocline (freshwater-seawater interface). This highly surface-active fraction of particulate organic matter can be viewed as oily droplets. SAP are fluid, and are readily transformed at interfaces to films of molecular thickness (surface area per particle is in the range 10⁻⁵–10⁻² cm²).Comparison of response of individual SAP with model particles, and the frequency of their appearance in estuarine samples, shows that a majority of estuarine SAP has, in terms of viscosity and film permeability, the properties of oleic acid. A significant fraction of SAP have more rigid structures, comparable to moleic acid + cholesterol model particles. A small fraction ( > 1%) behaves as phytoplankton cells with fluid outer membranes.We have also presented evidence for a strong interaction between elemental mercury and SAP, which is not sensitive to the molecular structure of the organic phase. The puzzling accumulation of mercury at the halocline of the Krka Estuary may be regarded as the result of interaction of elemental mercury with SAP.     

Logatchev热液场附近表层沉积物中有机质的组成特征、来源及其影响因素

利用2005年"大洋一号"科学考察船电视抓斗采样器采集的表层沉积物样品,对大西洋洋中脊Logatchev热液场附近7个站位表层沉积物样品中的烷烃组分进行了定量分析,并结合总有机碳(TOC)及C稳定同位素(δ13C值)分析,探讨了表层沉积物中有机质的组成及可能的来源和影响因素.结果表明:表层沉积物中正构烷烃组分以低碳数化...     

Early diagenesis of organic matter in Peru continental margin sediments: Phosphorite precipitation

Pore water chemistry (total dissolved CO₂, NH₄, NO₃, NO₂, PO₄, Si(OH)₄, Ca, Mg, Fe, Mn, SO₄, H₂S and F, and titration alkalinity), solid phase chemistry (C_org, P_org, C_TOT, N_TOT, F, Si_OPAL and S_II), and sediment characteristics (porosity, dry bulk density and formation factors) were determined on a centimeter-scale spacing in the upper 20–40 cm of sediments under intense upwelling areas on the Peru continental shelf. These data demonstrate that carbonate fluorapatite (CFA) is precipitating from pore waters in the upper few centimeters of a gelatinous mud with high organic carbon content (up to 20% C_org), very high porosity ( > 0.96 ml cm⁻³) and very low dry bulk density (< 0.1 g cm⁻³). Dissolved phosphate concentrations at the sediment-water interface range from 20 to 100 μM, orders of magnitude higher than bottom-water concentrations, and much higher than predicted from regeneration of organic matter. The mechanism of this interfacial phosphate release is unclear, but is apparently uncoupled from carbon and nitrogen metabolism and thus may be linked either to dissolution of fish debris or to the presence of a microbial mat in surficial sediments. Fluoride is incorporated into CFA by diffusion from the overlying seawater, and carbonate ions are provided from pore-water alkalinity. Magnesium concentrations in this reaction zone are not significantly different from those of seawater, suggesting that magnesium depletion is not a necessary prerequisite for CFA precipitation.

The environment of precipitation is interface-linked rather than driven by organic diagenesis of phosphorus deeper in the sediment. Most of the cores display a wide range of diagenetic characteristics below the immediate interfacial region, but almost all show the precipitation signature near the interface. This interface-linked early diagenetic porewater environment for the precipitation of CFA explains many of the geochemical characteristics of phosphorites and provides a “testable” model to compare the modern phosphogenic analog with ancient phosphorite deposits. Two of the cores display very high solid phase phosphorus and fluoride contents reflecting the presence of apparently modern pelletal apatites.     

Hydrocarbon pollution from marinas in estuarine sediments

A measure of the impact of marinas on three Eastern Virginia estuarine creeks was obtained by a study of hydrocarbons in their sediments. Two of the creeks support considerable marine activity, including pleasure boat marinas, boat repair facilities, and commercial fishing operations. The third creek, which served as a control, is seldom used by boats, and is surrounded by marsh and woodland.Sediments from the creeks with marinas contained significantly higher levels of both aromatic and aliphatic hydrocarbons than did the control. Differences in the concentrations of certain oil-pollution indicators, such as the 17α,21β-hopane homologs and phytane, and low molecular weight aromatic hydrocarbons, are indicative of light petroleum fractions. Most of the aromatic hydrocarbons from all creeks, however, appear to have a pyrogenic origin.Although hydrocarbons from three probable origins (petroleum, pyrogenesis, and recent biosynthesis) were detected in all locations, the petroleum-derived and pyrogenic hydrocarbons were of only minor importance relative to the biogenic hydrocarbons in the control creek.     

Isolation of dissolved organic matter and copper-organic complexes from estuarine waters using reverse-phase liquid chromatography

Reverse-phase liquid chromatography was used for the isolation of dissolved organic matter and dissolved copper-organic complexes from the estuarine waters of Narragansett Bay, Rhode Island. The procedure isolates 10–30% of the organic matter and up to 50% of the total dissolved copper from various bay samples. Chromatograms obtained by high-performance liquid chromatography of the isolated organic matter showed qualitative differences between sampling stations progressing from the Providence River in the upper bay to the lower bay.     

去除有机质前后海底沉积物对稀土元素吸附能力的变化研究

为更好地了解有机质对沉积物吸附稀土元素能力的影响,对珠江口和南海沉积物在去除有机质之前和之后进行了稀土元素吸附实验研究。结果表明,同一种沉积物在去除有机质前后对稀土元素的吸附呈现基本相同的规律,只是吸附量有所不同。沉积物在去除有机质之后对稀土离子的吸附能力比去除有机质之前大大降低;沉积物对各种稀土元素吸附量降低的百分比为:珠江口沉积物对Yb的吸附量减少了47.24%,对La的吸附量减少了75.50%,对其它元素的吸附量减少介于47.24%—75.50%之间;南海沉积物对Sm的吸附量减少了35.93%,对Ho的吸附量减少了45.41%,对其它元素的吸附量减少介于35.93%—45.41%之间。     

Particulate organic matter in the coastal and estuarine waters of Goa and its relationship with phytoplankton production

In the coastal and estuarine waters of Goa, particulate organic carbon (POC) varied from 0.52 to 2.51 mg l^?1 and from 0.28 to 5.24 mg l^?1 and particulate phosphorus (PP) varied from 0.71 to 5.18 μg l^?1 and from 0.78 to 20.34 μg l^?1, respectively. The mean values of chlorophyll and primary productivity were 1.94 mg m^?3 and 938.1 mg C m^?2 day^?1 in the coastal waters and 4.3 mg m^?3 and 636.5 mg C m^?1 day^?1 in the estuarine waters, respectively.$\text{POC}\text{chl}$ ratios were low in June and October even when POC values were quite high. The POC in surface waters was linearly correlated with the chlorophyll content. Also PP increased when chlorophyll and primary productivity remained high. The results suggest that the phytoplankton was sharply increasing and contributed to POC and PP content. The percentage of detritus calculated from the intercept values of chlorophyll on POC varied from 46 to 76% depending on season. Results indicate that the major portion of POC and PP during postmonsoon (October–January) is derived from phytoplankton production while the allochthonous matter predominate during monsoon (June–September).