The contribution of inorganic compounds to the particulate carbon,nitrogen, and phosphorus in suspended matter and surface sediments of Chesapeake Bay

Particulate carbon, nitrogen, and phosphorus samples from the water column and surficial sediments of the Maryland portion of Chesapeake Bay were thermally partitioned into their organic and inorganic components. During periods of both high and low fluvial input and high and low phytoplanktonic production, particulate organic carbon accounted for a mean of 99.3% of the total particulate carbon and particulate organic nitrogen accounted for a mean of 99.1% of the total particulate nitrogen. The particulate organic phosphorus contribution was variable both seasonally and spatially, accounting for 14–77% of the total pool of particulate phosphorus. The highest concentrations were found in the surface waters during maximum phytoplanktonic production and low fluvial input. The contribution of particulate inorganic phosphorus to the seston and to total particulate phosphorus decreased as distance from the primary fluvial source increased, reflecting a greater relative inclusion of particulate phosphorus in the biologically bound component in the higher salinity zone seaward of the turbidity maximum. Organic carbon and nitrogen constituted over 99% of the surficial sediment carbon and nitrogen, and organic phosphorus was 10–40% of the surficial sediment phosphorus.     

Pore water trace metal chemistry in polluted sediments of a tropical estuary of SE Brazil

The Sepetiba Bay is a shallow water body semi enclosed located on the west side of Rio de Janeiro City. Almost 80% of flesh water discharge, from the St Francisco canal, coming from the northern side of the bay develops an estuarine environment. Fishing and tourism are some of the most important economic activities in the area. During 35 years a zinc/cadmium smelter has polluted the bay. The objective of this investigation is to demonstrate the diagenetic processes and cadmium remobilization into pore water from the contaminated sediments. Two sites were selected to compare diagenetic processes. Site P1 is located next to domestic effluents discharge into the bay and approximately 20km away from the smelter. Site P2 is located near the same smelter and next to the Mazomba estuary, which is not influenced directly by domestic effluents. Peeper samplers of 25 cells with a resolution of 2.5 cm were deployed at both the sites. After a 3-weeks period of equilibrium, the pore waters were separated from the cells and analyzed immediately （within 24 h） for alkalinity, NH3 and reactive soluble phosphorus on a spectrophotometer. An ICP-AESΣH2S spectrometer was used to analyze Na, Mg, Li, Ba, Sr, Si, Fe and Mn. Total and labile dissolved Cd in pore waters were determined by differential-pulse stripping voltametry. The dissolved constituents in the pore waters have shown that the intensities of diagenetic reactions are different between sites. The reactions are stronger at site P1 site than at site P2, especially between 7.5 cm and 22.5 cm, which is evident by the organic rich sediment.     

Biomarkers in surface sediments from the Cross River and estuary system,SE Nigeria: Assessment of organic matter sources of natural and anthropogenic origins

Herein, lipid biomarker analysis is applied to surface sediments from the southeastern Niger Delta region for the quantitative determination of aliphatic lipids, steroids and triterpenoids in order to differentiate between natural (autochthonous vs. allochthonous) and anthropogenic organic matter (OM) inputs to this deltaic environment. This ecosystem, composed of the Cross, Great Kwa and Calabar Rivers, is receiving new attention due to increased human and industrial development activities and the potential effects of these activities impacting its environmental health. While the presence of low molecular weight n-alkanes (<C₂₂) and the fossil biomarkers pristane and phytane in all samples, are indicative of a minor petroleum related input, the total extractable organic component of the surface sediments of these rivers remains predominantly of a natural origin as characterized by the variety and predominance of lipid classes that are mainly derived from the epicuticular waxes of vascular plants and include n-alkanes, n-alkanols, n-alkan-2-ones, n-alkanoic acids, steroids and triterpenoids. In addition, recent OM inputs from microorganisms are indicated by the presence of lower molecular weight n-alkanoic acids (C_max = 16), while the major triterpenoids of the sediments, taraxerol and friedelin, and the major sterol, sitosterol, indicate recent OM inputs from vascular plants. Plankton-derived sterols, such as fucosterol and dinosterol, are also found in sediments from the Cross and Great Kwa Rivers and likely originate from autochthonous primary productivity. Furthermore, the coprosterols coprostanol and 24-ethylcoprostanol are present in most samples and indicate measurable anthropogenic contributions from domestic untreated sewage inputs and agricultural run-off, respectively. Of the three rivers studied, the Cross River system was excessively influenced by human and industrial development activities, including drivers such as urbanization and population center growth, land-use change to support agricultural production and animal husbandry, and petroleum exploration and production. These influences were found to be regionally specific as controlled by point sources of pollution based on the relative distributions measured and on the fact that the molecular characteristics of sedimentary OM were not distributed smoothly along a gradient.     

Pb isotope signatures of sediments from Guanabara Bay, SE Brazil: Evidence for multiple anthropogenic sources

Sediments from Guanabara Bay and two rivers were analyzed for Pb isotope composition. The results define linear groups interpreted as different sources of Pb. The samples from Iriri and Surui rivers present different Pb compositions probably resulting from two active pollutants which are transported in the waters to the Guanabara Bay, where they are mixed. The ²⁰⁶Pb/²⁰⁷Pb values of 1.151 and 1.091 presented here are in the range of Brazilian galena ore signature.     

Vertical variation of phosphorus forms in surface sediments from Wuli Bay, Taihu Lake, China

1IntroductionPhosphorus,an essential nutrient for the primaryproductivity in freshwater systems,is an important fac-tor controlling lacustrine eutrophication.Although ex-ternal input of phosphorus has been assumed as the vi-tal responsibility for the eutrophication of lakes(ZhuJun et al.,2005),the remobilization of phosphorus insediments has a distinct influence on it as well(Bostr m et al.,1982).The concentrations of totalphosphorus(Ptotal)in the sediments are often related tothe trophic st…     

Minor elements in sediments of Great Bay estuary,New Hampshire

Concentrations of copper, zinc, chromium, lead, cadmium, and phosphorus were obtained from 81 samples of unconsolidated estuarine sediment from Great Bay, New Hampshire. Dispersal of aqueous chromium from localized industrial effluent is believed responsible for an increase in sediment chromium throughout the entire estuary. High phosphorus concentrations exist in sediment near the outfalls from several waste-water treatment plants. There is no evidence for any increase of copper, zinc, lead, or cadmium in this estuary, except for localized high concentrations close to industrial outfalls. Fine-grained sediments and organic carbon correlate highly with all the elements studied, except for chromium. This suggests that conventional agents of sedimentary adsorption are not adequate to explain the incorporation of chromium into sediment under the conditions of heavy industrial discharge which exist in this estuary. Sediment phosphorus correlates highly with minor elements, suggesting that it is an adsorption agent, similar to more typical sedimentary parameters such as organic matter and clay minerals. In such a capacity phosphorus may enhance the sedimentary uptake of other aqueous species, and account for higher chromium sediment concentrations. Comparative data from other sedimentary environments emphasize the environmental significance of these elements in Great Bay.     

Nutrient cycling in the sub-tropical Brunswick estuary,Australia

A combination of mixing plots, one-dimensional salt balance modelling, nutrient loading budgets, and benthic flux measurements were used to assess nutrient cycling pathways in the enriched sub-tropical Brunswick estuary during different freshwater flows. A simple model accounting for freshwater residence times and nutrient availability was found to be a good predictor of phytoplankton biomass along the estuary, and suggested that biomass accumulation may become nutrient-limited during low flows and that recycling within the water column is important during blooms. Dissolved inorganic nitrogen (DIN) cycling budgets were constructed for the estuary during different freshwater flows accounting for all major inputs (catchment, sewage, and urban) to the estuary. Internal cycling due to phytoplankton uptake (based on measured biomass) and sediment-water fluxes (based on measured rates in each estuarine reach) was considered. Four different nutrient cycling states were identified during the study. In high flow, freshwater residence times are less than 1 d, internal cycling processes are bypassed and virtually all dissolved, and most particulate, nutrients are delivered to the continental shelf. During the growth phase of a phytoplankton bloom enhanced recycling occurs as residence times increase sufficiently to allow biomass accumulation. Remineralization of phytoplankton detritus during this phase can supply up to 50% of phytoplankton DIN demands. In post-bloom conditions, DIN uptake by phytoplankton decreases in the autumn wet season when biomass doubling times begin to exceed residence times. OM supply to the sediments diminishes and the benthos becomes nutrient-limited, resulting in DIN uptake by the sediments. As flows decrease further in the dry season, there is tight recycling and phytoplankton blooms, and uptake by the sediments can account for the entire DIN loading to the estuary resulting in complete removal of DIN from the water column. The ocean is a potentially important source of DIN to the estuary at this time. The results of the DIN cycling budgets compared favorably with mixing plots of DIN at each time. The results suggest that a combination of different approaches may be useful in developing a more comprehensive understanding of nutrient cycling behavior and the effects of nutrient enrichment in estuaries.     

Fractionation of phosphorus in the sediments of a tropical estuary

Fractionation of phosphorus in the sediments of the Cochin estuary situated along the southwest coast of India was studied by applying sequential chemical extraction. The different forms of phosphorus were estimated seasonally (premonsoon, monsoon, and postmonsoon) under eight different schemes. The major forms of phosphorus analyzed were exchangeable P, anion exchangeable P, carbonate-bound P, labile and resistant organic P, Fe and Al P, calcium-bound P, and hydrolyzable surplus P. Quantitatively, the above fractions in isolation or in combination vary in content due to chemoestuarine variability and seasonal fluctuations. Changes in speciation have been noted in association with salinity variations in the waterway, especially following enhanced river runoff during the monsoon. The chemical forms of the sediment-bound phosphorus in the northern parts of this estuary have been shown to be modified by nonpoint sources. Sediment P fractionation defines the role of chemical speciation of phosphates (as nutrients) and is indicative of the processes controlling the pathways of P into the coastal waters. The changes in the exchangeable P, together with marked regional variations in calcium-bound P, exemplify the complex estuarine variability of phosphorus. Enhanced amounts of exchangeable P mark its appearence in high saline waters, signifying the presence of biologically available nutrient phosphorus. The calcium-bound P and hydrolyzable surplus P show significant relation with sediment organic carbon and Fe whereas other forms do not exhibit any marked covariation. The Ca and Na NTA extraction scheme is very specific in its selectivity.     

Heavy metal accumulation in mangrove sediments surrounding a large waste reservoir of a local metallurgical plant, Sepetiba Bay, SE, Brazil

Due to the growing rate of urbanization and a rapid and unplanned development in many tropical coastal areas, there continues to be an increasing concern in relation to the impact of anthropogenic activities on mangrove sediments. In southeastern Brazil, the Sepetiba Bay becomes an example of an ecosystem in the process of accelerated degradation. Previous studies highlighted the activities related with zinc processing by an industry on the Madeira’s Island as one of the main source of heavy metal to Sepetiba Bay. Despite the end of the industrial activities in the area, the waste reservoir became the main source of pollutant to the surrounding area. Analyses of Cd, Pb, Cu, Cr, Hg, Ni, Zn, particle size and nutrients of 20 sediment samples collected in the mangrove of the Madeira Island showed that the waste reservoir is the main source of contaminant to the mangrove. The statistic analyses showed that the moisture content and organic matter play an important role in the geochemical dynamic of heavy metal in the area.     

Separation of total nitrogen from sediments into organic and inorganic forms for isotopic analysis

Nitrogen isotopic (δ¹⁵N) analysis is widely applied in palaeoceanography, palaeolimnology and soil science. Most measurements are performed on untreated bulk samples containing both organic and inorganic nitrogen (ON and IN), which could sometimes confound isotopic signals. Here we propose a sample pretreatment method to physically and quantitatively separate the total nitrogen into ON and IN for subsequent concentration and isotopic measurements. In the method, the sediment is first demineralized with HCl and HCl-HF, adsorbed and bound IN being liberated into the acid solutions during the demineralization. Then, organic matter (OM) dissolved in the acid solutions is recovered by a sorbent of styrene divinyl benzene polymer (Bond Elut PPL, Varian) and is then combined with the acid-resistant OM to obtain the total OM. Finally, IN in the acid solutions passing through the PPL sorbent is recovered by way of steam distillation. Total nitrogen recovery with the method is 92.4% and isotopic mass balance calculations show that the δ¹⁵N value of total nitrogen can be quantitatively partitioned into the organic and inorganic forms. The δ¹³C values of the separated OM show a small positive excursion of 0.2‰ relative to those of bulk OM, ruling out significant loss of ON during the pretreatment. By comparison, the KOBr method, widely used to remove ON from bulk samples for isotope measurements, gives lower IN concentration and higher δ¹⁵N_IN values, attributed to the partial loss of IN and escape of some oxidation-resistant ON.     

Origin of rare earth element anomalies in mangrove sediments,Sepetiba Bay,SE Brazil: used as geochemical tracers of sediment sources

Elemental contents were determined in two mangrove habitats along Sepetiba Bay, SE Brazil, an area impacted by local industrial activities, as well as hinterland water diversion networks. This study demonstrates how specific REEs (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu) may be used as a sediment source tracer to mangrove-dominated coastlines. From the two stations studied, a pair of cores was collected, one in the mangrove forest and the other in the tidal flat. Station 1 results show a general enrichment in most of the fractioned patterns of the REEs normalised by Post-Archean Australian Shale. The relatively light rare earth elements are similarly enriched in the generally more polluted Station 1. Despite the probable difference in background sediment characteristics, a common sharp increase in mud contents patterns in the upper part of the mangrove sediment core was related to a lower REE content as well as Eu anomalies. With existing knowledge of clockwise water circulation in the bay, these patterns can be explained by man-made water diversion from the São Francisco and Guandu rivers, initiated more than 30 years ago, whereby suspended matter with relatively large contents of REEs and material originating from industrial sources accumulate in the eastern sector of the bay. This is the first comprehensive assessment of REEs as sedimentary tracers in a mangrove ecosystem in Brazil.     

Patterns of organic and inorganic sulfur transformations in sediments

Two new methods for analysis of sedimentary sulfur employing sensitive flame photometric detection have been developed and applied to a study of marine, estuarine and freshwater sediments. Volatile organosulfur compounds generated from freeze-dried sediments upon heating in a H₂ atmosphere reflect the distribution and extent of degradation of detrital organic matter. Regions of biogeochemical sulfur transformations, as characterized by the presence of SO₂ progenitors, sulfite and thiosulfate, are also depicted. Scrubbing of sediment slurries treated with the reducing agent, acidic Cr(II) solution, releases H₂S and CH₂SH from their metal-complexed forms. CH₃SH is a common constituent of marine and estuarine sediments at sub-ppm concentrations.     

Volatile C1-C7 organic compounds in surface sediments from Walvis Bay

C₁-C₇ volatile organic compounds were analyzed in three gravity cores taken from Walvis Bay shelf. The compounds detected included alkanes (methane, ethane, propane, i- and n-butane, and i- and n-pentane, and heptane), alkenes (2-methyl-2-butene, dimethylcyclopentenes, cyclohexene), oxygen containing compounds (2- and 3-methylfuran, 2,5-dimethylfuran, 2- and 3-methylbutanal and 3-pentanone), sulfur compounds (dimethylsulfide, thiophene, 2- and 3-methylthiophene) and aromatic compounds (benzene and toluene). In situ biological and low temperature chemical (less than 15°C) formation processes are proposed, possibly from marine terpene precursors. Subsequent to this work, these compounds were found to be widely distributed in surface gravity cores from other areas. Many of these compounds do not survive deeper burial. Furans, ketocompounds, and alkenes are generally not found in more than trace quantities in deeper (?10m subbottom) DSDP cores we have examined from other areas.     

Trace elements in surface sediments of Navarino Bay,Greece

The distribution of a number of trace elements in the Navarino Bay surface sediments is examined and their source and association with the major phases is determined. Cobalt follows Al in its distribution, having its highest vaues towards the center and deeper parts of the bay; Zn and Cu have their highest values at the effluent outfalls of a distillery and an olive oil and olive kernel factory (at the port of Yalova), being decreased away. The highest concentration of Ni is found near the town Pylos, while the highest concentrations of Rb and Y are observed at the mouths of rivers Yalovas and Xerias. Organic matter has its highest content at the port of Pylos, while no significant variations have been observed in the distribution of Sn and Ga. It is demonstrated that there is an anthropogenic input of Zn, Cu, and Corg in the bay. Zn and Cu are discharged by a distillery and an olive oil and olive kernel factory, at Yalova. Organic matter is mainly derived from domestic sewage. Ni enters the bay from its southern coasts and might be derived from weathering of bauxite deposits present in the adjacent limestones. Rb and Y are transported by the rivers Yalovas and Xerias from the northeastern adjacent land area; Ni, Co, and Cu show positive correlation with Al, suggesting their incorporation in clay minerals, while Rb shows positive correlation with Si, suggesting its incorporation in silicate detrital minerals. The following areas in the bay are considered to be heavily polluted: (1) the port and a large zone near Pylos (domestic sewage); (2) the port and a small area near Yalova (domestic sewage and industrial effluents); and (3) the eastern coast of the island Sphaktiria (oil). The domestic sewage pollution in Navarino Bay is of the same level as that in other Greek bays.     

Biogeochemistry of fatty acids in recent sediments from Narragansett Bay,Rhode Island

The fatty acid composition of sediments from Narragansett Bay show significant variation between certain areas of the Bay. Both the organic carbon and fatty acid concentrations decrease with increasing distance from the Providence River area—an area which received municipal sewage and industrial effluents. The ratio of the fatty acid concentration to organic carbon concentration is fairly constant for all stations sampled. The variations in the relative abundance of fatty acids may reflect either the influence of fatty acids discharged to the river area by sewage effluents or the synthesis of fatty acids by microbial populations which probably differ for the areas compared. Temporal variations in fatty acid composition and fatty acid concentration are minimal. Lipolytic activity has been demonstrated and probably acts on glycerides deposited to the sediments releasing free fatty acids shortly after deposition. A model for the diagenesis of fatty acids in Recent sediments is proposed based upon the above findings and upon earlier reports by the authors and by other investigators.     

Plankton and dissolved inorganic carbon isotopic composition in a river-dominated estuary: Apalachicola Bay, Florida

To characterize the isotopic composition of organisms at the base of the food web and the controls on their variability, the concentration and δ¹³C isotopic composition of dissolved inorganic carbon (DIC) and plankton δ¹³C, δ¹⁵N, and δ³⁴S were measured. The measurements were made during periods of high and low river flow in Apalachicola Bay, Florida, United States, over 3 yr. DIC concentration and δ¹³C values were related to salinity, indicating that conservative mixing of riverine and marine waters was responsible for the overall distributions. The usefulness of DIC δ^13C data for characterizing the trophic processes within the estuary was dependent upon the residence time of water within the season. Plankton δ¹³C values varied from −22‰ to −30‰ and were directly related to estuarine DIC δ¹³C, offset by a factor of roughly −20‰. This offset factor varied with salinity. Values of δ³⁴S in estuarine plankton (station means ranged from 11.4‰ to 13.1‰) were depleted relative to marine plankton (17.7±0.4‰) possibly due to the admixture of³⁴S-depleted sedimentary sulfide with estuarine samples. Values of δ³⁴S in plankton were not related to δ¹³C values of plankton and were only weakly correlated to the salinity of the water from which the plankton were collected, indicating that marine sulfate was the primary source of planktonic sulfur. Values of δ¹⁵N in plankton varied from 5.5‰ to 10.7‰ and appeared related to dominance of the sample by phytoplankton or zooplankton. Estuarine plankton was¹⁵N enriched relative to offshore plankton and estuarine sediment.     

Sources and transformations of organic matter in surface soils and sediments from a tidal estuary (North Inlet, South Carolina, USA)

Surface soil and sediment samples collected along a forest-brackish marsh-salt marsh transect in a southeastern U.S. estuary were separated into three different fractions (sand, macro-organic matter, and humus) based on size and density. Elemental, stable carbon isotope, and lignin analyses of these samples reveal important contrasts in the quantity, composition, and sources of organic matter, between forest and marsh sites. Elevated nitrogen contents in humus samples suggest nitrogen incorporation during humification is most extensive in forest soils relative to the marsh sites. The lignin compositions of the macro-organic and humus samples reflect the predominant type of vegetation at each site. Lignin phenol ratios indicate that woody and nonwoody litter from, gymnosperm and angiosperms trees (pines and oaks) is the major source of vascular plant-derived organic matter in the forest site and that angiosperm, grasses (Juncus andSpartina) are the major sources of lignin at the marsh sites. The phenol distributions also reveal that oxidative degradation of lignin is most extensive in the forest and brackish marsh zones whereas little lignin decay occurs in the salt marsh samples. In forest soils, most organic matter originates from highly altered forest vegetation while at the brackish marsh site organic matter is a mixture of degradedJuncus materials and microbial/algal remains. Organic matter in the salt marsh appears to be composed of a more complex mixture of sources, including degradedSpartina detritus as well as algal and microbial inputs. Microbial methane oxidation appears to be an important process and a source of¹³C depleted organic carbon in subsurface sediments at this site.     

Spatial and temporal variations in terrestrially-derived organic matter from sediments of the Delaware estuary

Terrestrially-derived organic matter in sediments of the Delaware Estuary originates from riverine transport of soils and fresh litter, sewage and industrial wastes, and marsh export of organic matter. The quantity, composition, and spatial distribution of terrigenous organic matter in sediments was determined by elemental (C and N), lignin, and stable carbon isotope analyses. Sediments in the upper Delaware Estuary had low organic carbon content and high lignin content. In contrast, sediments in the lower Delaware Estuary had high organic carbon content and low lignin content. There was a slight decrease in the proportion of syringyl and cinnamyl phenols relative to vanillyl phenols between the upper estuary and lower estuary. Differences in lignin and stable carbon isotope compositions between sediments of the Delaware Estuary and sediments of the Broadkill River estuary (an adjoining salt-marsh estuary) supported previous observations that marshes do not export substantial quantities of organic matter to estuaries. Additional results suggested that lignin-rich sediments were concentrated in the upper estuary, most likely in the zone of high turbidity. Furthermore, algal material diluted lignin-rich sediments, particularly in the lower estuary. The weaker algal signal in bottom sediments compared to that in suspended particulate matter suggested algal material was decomposed either in the water column or at the sediment-water interface. Physical sorting of sediments prior to deposition was also indicated by observations of compositional differences between the upper and lower estuary bottom sediments. Finally, seasonal variations in primary productivity strongly influenced the relative abundance of terrestrial organic matter. In fall, however, the proportion of lignin was greatest because of a combination of greater inputs of terrestrially-derived organic matter, lower river discharge, and a decrease in algal biomass.     

Heavy metal concentrations in water and surface sediments of Maharlou Lake, SE of Shiraz, Iran

The main objective of this study is to evaluate trace metal distribution and identify their sources in the Maharlou Lake. Trace metals （Cr, Co, Ni, Cu, Zn, Cd, Pb） and major elements （A1, Ca, Fe, K, Mg, Mn, Na, P） were investigated in water and surface sediments. There was a negative relationship between the depth of water and heavy metal concentration. Metal concentrations in water and sediment samples show a high variability and decrease in this order： Al〉Fe〉Ni〉Co〉Pb〉Zn〉Cu〉Mn〉Cd. In the northern parts of the lake, especially at the inflow of drains and the Khoshk River of Shiraz City, metal concentrations are higher in both water and sediment samples. In order to assess the heavy metal enrichment in sediment samples, trace metal concentrations were normalized for Al. Except for Mn, all metals are enriched relative to average crust and average sedimentary rocks. Also, the results showed that stations located at the northern coast of the lake, have higher enrichment factors （EF） than the other stations. The results of this study showed that the Khoshk River and other drains are the main pollutant sources of the Maharluo Lake.