Contaminants in sediments from the central Gulf of Mexico

Surface sediment samples at 89 locations and 300-cm cores from 43 sites in the Mississippi Sound were examined for evidence of pollutant impact upon this coastal environment. Chemical variables determined were total organic carbon, Kjeldahl nitrogen, phenols, and hydrocarbons. Values of these pollutant indicators were about the same or lower in Gulf of Mexico samples compared to Missippi Sound sediments and considerably lower than those from rivers and bays emptying into the sound, indicating limited impact from sites of pollutant sources into the sound. Concentrations of sedimentary pollutants peaked in the Pascagoula River where levels of total organic carbon (TOC), Kjeldahl nitrogen (TKN), phenols, and hydrocarbons exceeded sound values by one to three orders of magnitude. Analysis of cores shows pollutant intrusion to sediment strata predating industrial development. The level of pollution varies from site to site but fortunately is only serious at localized sites within the sound.     

Sources and distribution of terrigenous organic matter delivered by the Atchafalaya River to sediments in the northern Gulf of Mexico

Suspended sediments (SS) from the Atchafalaya River (AR) and the Mississippi River and surficial sediment samples from seven shallow cross-shelf transects west of the AR in the northern Gulf of Mexico were examined using elemental (%OC, C/N), isotopic (δ¹³C, Δ¹⁴C), and terrigenous biomarker analyses. The organic matter (OM) delivered by the AR is isotopically enriched (∼−24.5‰) and relatively degraded, suggesting that soil-derived OM with a C4 signature is the predominant OM source for these SS. The shelf sediments display OC values that generally decrease seaward within each transect and westward, parallel to the coastline. A strong terrigenous C/N (29) signal is observed in sediments deposited close to the mouth of the river, but values along the remainder of the shelf fall within a narrow range (8-13), with no apparent offshore trends. Depleted stable carbon isotope (δ¹³C) values typical of C3 plant debris (−27‰) are found near the river mouth and become more enriched (−22 to −21‰) offshore. The spatial distribution of lignin in shelf sediments mirrors that of OC, with high lignin yields found inshore relative to that found offshore (water depth > 10 m).The isotopic and biomarker data indicate that at least two types of terrigenous OM are deposited within the study area. Relatively undegraded, C3 plant debris is deposited close to the mouth of the AR, whereas more degraded, isotopically enriched, soil-derived OM appears to be deposited along the remainder of the shelf. An important input from marine carbon is found at the stations offshore from the 10-m isobath. Quantification of the terrigenous component of sedimentary OM is complicated by the heterogeneous composition of the terrigenous end-member. A three-end-member mixing model is therefore required to more accurately evaluate the sources of OM deposited in the study area. The results of the mixing calculation indicate that terrigenous OM (soil-derived OM and vascular plant debris) accounts for ∼79% of the OM deposited as inshore sediments and 66% of OM deposited as offshore sediments. Importantly, the abundance of terrigenous OM is 40% higher in inshore sediments and nearly 85% higher in offshore sediments than indicated by a two-end-member mixing model. Such a result highlights the need to reevaluate the inputs and cycling of soil-derived OM in the coastal ocean.     

Normalization of metal concentrations in estuarine sediments from the Gulf of Mexico

Metal concentrations were examined in sediments from 497 sites within the estuaries of the Gulf of Mexico by the United States Environmental Protection Agency's Environmental Monitoring and Assessment Program (EMAP). Data were normalized for extant concentrations of aluminum to isolate natural factors from anthropogenic ones. The normalization was based on the hypothesis that metal concentrations vary consistently with the concentration of aluminum, unless metals are of anthropogenic origin. Strong linear correlations (>75% variation explained) were observed between Al and Cr, Cu, Pb, Ni, and Zn. Moderate correlations (50–75% variation explained) were observed between Al and As or Ag. Weak but significant correlations (30–40% variation explained) were observed between Al and Hg or Cd. Based on these results, the spatial extent of contamination was examined. About 39% of sites with contamination by at least one metal occurred near population centers, industrial discharge sites, or military bases. The remainder of the observed contamination represented a dispersed pattern, including the lower Mississippi River (7%) and numerous agricultural watersheds (54%), suggesting that the contamination might be from nonpoint sources.     

墨西哥湾含水合物和油气渗漏区海底表层沉积物中有机质饱和烃组成分布特征研究

报道了采自墨西哥湾富含水合物和油气渗漏区6个海底表层沉积物样品中有机质的丰度、组成和分布特征.研究发现,所分析的6个沉积物样品中有机质的丰度和组成变化很大,其中S-1、S-7和S-9样品中饱和烃的组成分布主要反映了现代海洋沉积有机质及其受细菌微生物改造作用的特征,而S-8、S-10和S-11样品中饱和烃组成以特征的石油污染成因的不可分辨的混合物(UCM)为主,相关甾萜类参数也表明沉积物受到原油渗漏或泄露污染;另一方面,S-8和S-11样品中正构烷烃不同程度的缺失表明有机质遭受了较为强烈的的生物降解作用.仅在S-1沉积物中鉴定出了与甲烷古细菌厌氧氧化有关的特征标志物--2,6,10,15,19-五甲基二十烯烃系列化合物(PMI△)并且具有极负的碳同位素组成,这表明S-1样品所在海底可能有天然气水合物的产出.     

The distribution of dibenzothiophenes in Gulf of Mexico sediments

Sediment extracts from 81 piston cores taken in water depths between 70 and 1200 m on the Gulf of Mexico continental shelf and slope were analyzed for dibenzothiophenes by capillary gas chromatography with flame photometric detection (FPD). The major aromatic sulfur compounds detected were dibenzothiophene; methyl, ethyl and propyl dibenzothiophenes; two unidentified sulfur compounds; and a series of benzothiophenes. In general, benzothiophenes (BTs) were detected at only trace levels though this may be due to loss during the analysis. Dibenzothiophenes (DBTs) concentrations ranged from <1 to 1725 ng/g, with an average of 139 ng/g. Vertical distributions generally showed significant increases in DBTs concentrations with depth. DBTs distributions in sediment extracts were similar to oils produced in the northern Gulf of Mexico. Variations from this composition may be due to microbial degradation in the near subsurface. The vertical and molecular distribution of DBTs suggests that the source of DBTs in the Gulf of Mexico sediments studied is upward migrating petroleum. Two unidentified compounds are speculated to be derivatives of DBTs, caused by indigenous microbial activity. This study suggests that DBTs may be useful for detecting seepage from deeper, more mature, source rocks and/or reservoired petroleum.     

Heavy metals in sediments from San Antonio Bay and the northwest Gulf of Mexico

Sediments from San Antonio Bay, the northwest Gulf of Mexico, and the Mississippi River Delta were acid leached and analyzed for Fe, Mn, Pb, Zn, Cd, Cu and Ni by atomic absorption spectrophotometry. In order to account for differences in sediment clay, carbonate, and organic matter content, metal concentrations were normalized to Fe. Significant linear correlations of metals to Fe were obtained for unpolluted sediments and deviations from these “natural” statistical populations were found for areas thought to have metal input caused by man. San Antonio Bay sediments show little evidence of metal pollution despite 70 years of shell dredging in the bay. However, the San Antonio-Guadalupe River system, the bay's prime sediment source, has 10% to 50% higher than natural levels of Pb, Cd and Cu. Sediments from a 1500 km² area of the Mississippi River Delta have Pb and Cd concentrations 10% to 100% higher than expected levels. The vertical distribution of Pb and Cd in these sediments suggests that inputs have occurred during the past 30 to 40 years. We find no indication of metal pollution in other areas of the Delta or along the continental shelf of the northwest Gulf of Mexico.     

Organic carbon isotope ratios of recent sediments from coastal lagoons of the Gulf of Mexico,Mexico

The stable carbon isotope composition sedimentary organic carbon was determined in the sediments of seven coastal lagoons of the Gulf of Mexico, Mexico. For most of the lagoons the δ¹³C values for sediments ranged from ?20.1 to ?23.9%. Anomalously low values, ?26.8 to 29.3%. were determined in sediments of two of the studied lagoons, probably due to the presence of organic carbon from anthropogenic sources, naturally absent in these environments. The δ¹³C values determined in the tissues of oysters collected at the same time in the different lagoons were very similar to those recorded in the sediments.     

Characterization of organic matter in surface sediments of the Mackenzie River Basin, Canada

The particulate organic matter in < 63 µm surface sediments from the Mackenzie River and its main tributaries was studied using Rock-Eval pyrolysis and organic petrology. The organic matter in the sediments is dominated by refractory residual organic carbon (RC) of mainly terrigenous nature, as indicated by abundant inertinite, vitrinite, and type III kerogen. Sediments from the tributaries contained significantly more algal-derived organic matter than from the main channel of the river, highlighting the importance of low-energy system dynamics in the tributaries, which allows modest algal production, more accumulation, and better preservation of autochthonous organic matter. This is particularly true for tributaries fed by lacustrine systems, which showed the highest S1 and S2 fractions, and consequently higher total particulate organic carbon (POC) in the basin. Organic petrology of the sediment samples confirms abundant liptinitic materials (i.e., fat-rich structured algae, spores and pollen, cuticles, and resins). Forest fire and coal deposits are also confirmed to contribute to the basin. Assuming that suspended and fine surfacial sediments have a similar OC composition, the Mackenzie River is estimated to deliver a total POC flux of 1.1 Mt C/yr to its delta, of which 85% is residual carbon with liptinitic OC (S1 + S2) and S3 accounting for another 9% and 6%, respectively.     

Tidal pumping drives nutrient and dissolved organic matter dynamics in a Gulf of Mexico subterranean estuary

We hypothesize that nutrient cycling in a Gulf of Mexico subterranean estuary (STE) is fueled by oxygen and labile organic matter supplied by tidal pumping of seawater into the coastal aquifer. We estimate nutrient production rates using the standard estuarine model and a non-steady-state box model, separate nutrient fluxes associated with fresh and saline submarine groundwater discharge (SGD), and estimate offshore fluxes from radium isotope distributions. The results indicate a large variability in nutrient concentrations over tidal and seasonal time scales. At high tide, nutrient concentrations in shallow beach groundwater were low as a result of dilution caused by seawater recirculation. During ebb tide, the concentrations increased until they reached a maximum just before the next high tide. The dominant form of nitrogen was dissolved organic nitrogen (DON) in freshwater, nitrate in brackish waters, and ammonium in saline waters. Dissolved organic carbon (DOC) production was two-fold higher in the summer than in the winter, while nitrate and DON production were one order of magnitude higher. Oxic remineralization and denitrification most likely explain these patterns. Even though fresh SGD accounted for only ∼5% of total volumetric additions, it was an important pathway of nutrients as a result of biogeochemical inputs in the mixing zone. Fresh SGD transported ∼25% of DOC and ∼50% of total dissolved nitrogen inputs into the coastal ocean, with the remainder associated with a one-dimensional vertical seawater exchange process. While SGD volumetric inputs are similar seasonally, changes in the biogeochemical conditions of this coastal plain STE led to higher summertime SGD nutrient fluxes (40% higher for DOC and 60% higher for nitrogen in the summer compared to the winter). We suggest that coastal primary production and nutrient dynamics in the STE are linked.     

Mineralogy,geochemistry, and radiocarbon ages of deep sea sediments from the Gulf of Mexico,Mexico

The mineralogy, geochemistry, and radiocarbon ages of two sediment cores (GMX1 and GMX2) collected from the deep sea area of the Southwestern Gulf of Mexico (∼876–1752 m water depth) were studied to infer the sedimentation rate, provenance, heavy metal contamination, and depositional environment. The sediments are dominated by silt and clay fractions. The mineralogy determined by X-Ray diffractometry for the sediment cores reveals that montmorillonite and muscovite are the dominant clay minerals. The sections between 100 and 210 cm of the sediment cores GMX1 and GMX2, respectively, are characterized by the G. menardii group and G. Inflata planktonic foraminiferal species, which represent the Holocene and Pleistocene, respectively. The radiocarbon-age measurements of mixed planktonic foraminifera varied from ∼268 to 45,738 cal. years B.P and ∼104 to 25,705 cal. years B.P, for the sediment cores GMX1 and GMX2, respectively. The variation in age between the two sediment cores is due to a change in sediment accumulation rate, which was lowest at the location GMX1 (0.006 cm/yr) and highest at the location GMX2 (0.017 cm/yr).The chemical index of alteration (CIA), chemical index of weathering (CIW), and index of chemical maturity (ICV) values indicated a moderate intensity of weathering in the source area. The total rare earth element concentrations (∑REE) in the cores GMX1 and GMX2 vary from ∼94 to 171 and ∼78 to 151, respectively. The North American Shale Composite (NASC) normalized REE patterns showed flat low REE (LREE), heavy REE (HREE) depletion with low negative to positive Eu anomalies, which suggested that the sediments were likely derived from intermediate source rocks.The enrichment factor of heavy metals indicated that the Cd and Zn concentrations in the sediment cores were impacted by an anthropogenic source. The redox-proxy trace element ratios such as V/Cr, Ni/Co, Cu/Zn, (Cu + Mo)/Zn, and Ce/Ce* indicated that the sediments were deposited under an oxic depositional environment. The similarity in major element concentrations, REE content, and the NASC normalised REE patterns between the cores GMX1 and GMX2 revealed that the provenance of sediments remained relatively uniform or constant during deposition for ∼4.5 Ma. The major and trace element based multidimensional discrimination diagrams showed a rift setting for the core sediments, which is consistent with the geology of the Gulf of Mexico.     

Dissolved organic matter in pore water of carbonate sediments from Bermuda

Pore water samples from seven nearshore areas in Bermuda were obtained under in situ conditions and analyzed for dissolved organic carbon, dissolved carbohydrates, dissolved free amino acids and dissolved humic substances. The concentration of dissolved organic carbon is higher than in the overlying nearshore waters indicating significant diagenetic remobilization of carbon in these recently deposited carbonate sediments. Dissolved carbohydrates decrease with depth due to microbial utilization.     

The nature and distribution of organic matter in the surface sediments of world oceans and seas

Existing data on the distribution of organic carbon and nitrogen in marine sediments have been analyzed in order to better understand the physical and chemical processes involved in this aspect of the global carbon cycle. Maps of the global distribution of organic carbon and nitrogen in the sediments of world oceans and seas are presented.Correlation analyses of the available information dealing with the distribution of marine sedimentary organic matter has revealed that in terms of bulk parameters (%C_Org and %N Kjeldahl), there is an apparent accumulation of organic matter on the continental slope (water column depth 200–2000 m). Specific interactions between clays and organic matter, although indicated in laboratory experiments, have not been detected by these analyses.     

Concentrations of elements and metals in sediments of the southeastern Gulf of Mexico

. This paper deals with the extent of contamination in sediments of the southeast Gulf of Mexico. The concentration of elements (SiO2, Al2O3, Fe2O3, Na2O, MgO, CaO, and K2O) and heavy metals (Cu, Cd, Zn, Co, Pb, Ag, Cr, Ni, V, and Ba) were determined. The elemental composition of sediments is influenced by the Grijalva–Usumacinta–Terminos System at the east and the Tabasco lagoon system (El Carmen–La Machona) at the west coast of the study area. Concentrations of Ni, V, and Ba were anomalously high at some sites. Oil production activities in the vicinity of the sites may be responsible for the high values. Correlations of metal concentrations to elemental composition were performed. No significant relationships between metals and elements were found for most metals (p>0.05), suggesting that metals are not significantly associated with naturally occurring aluminosilicates, iron hydroxide, and calcium carbonate minerals of sediments. Other sources such as organic matter may be contributing to the total concentration of metals. The comparison of metal content in sediments of the southeast Gulf of Mexico with metals of the other areas of the Gulf of Mexico suggests that it is relatively contaminated with Cd, Pb, and Ni. The probable causes of contamination are briefly discussed.     

Organic and organometallic compounds in estuarine sediments from the Gulf of Mexico (1993–1994)

Sediment samples from 281 estuarine sites in the Gulf of Mexico were collected in 1993–1994 and analyzed for several classes of organic and organometallic compounds as part of the Environmental Monitoring and Assessment Program of the United States Environmental Protection Agency. Polynuclear aromatic hydrocarbons (PAHs) were the contaminant class found most frequently and in the highest concentrations; the sum of 24 congeners (ΣPAHs) ranged from <5 ng g^?1 to 15.500 ng g^?1 (dry wt basis). A low percentage of samples (3.9%) exceeded 2000 ng g^?1 ΣPAHs, and only six samples (2.1%) exceeded 4000 ng g^?1, a level above which adverse biological effects may be expected to occur. Less than 4% of sediments exceeded 20 ng g^?1 for the sum of 20 polychlorinated biphenyls (ΣPCBs) and only four samples (1.4%) exceeded 20 ng g^?1 for the sum of several organochlorine pesticides (ΣOCPs). A sample from Freeport Harbor, Texas, contained 4230 ng g^?1 ΣPAHs, 322 ng g^?1 ΣPCBs, and 49.6 ng g^?1 ΣOCPs. Tributyltin exceeded 100 ng g^?1 in only four samples, all of which were from stations in Corpus Christi Bay or Galveston Bay in Texas. The detection of a suite of organophosphate pesticides was very rare and did not exceed 15 ng g^?1. Sediments from the tidally influenced section of the Mississippi River in Louisiana contained low to moderate levels of all classes of organic compounds. The most contaminated sites were in urban estuaries (e.g., Corpus Christi, Galveston, and Pensacola (Florida bays), underscoring the need to concentrate future monitoring and assessment efforts at the regional and local level.     

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.     

10Be meltwater signal in Orca basin sediments,Gulf of Mexico

An increase in the cosmogenic beryllium-10 content of the Orca basin sediments due to the flooding of the Gulf of Mexico (GM) by meltwaters during the late Wisconsin interglacial is reported. A strong negative correlation (γ =-0.99) betweenδ ¹⁸ O (in the range o f-1.5‰ to +0.5‰) and¹⁰Be/Al ratio is seen. During intense flooding reflected by a decrease in δ¹⁸O by ∼ 2‰, this correlation may not hold as some of the sediments with low¹⁰Be/Al ratio and deposited on the shelf and slope regions of the GM during the earlier glacial period would also be washed into the basin. The deposited sediment would then be a mixture with a¹⁰Be/Al ratio lower than expected from the correlation     

近岸沉积物再悬浮期间所释放溶解有机物的荧光特征

对采自厦门湾九龙江人海河口的4个沉积物样品进行了室内再悬浮模拟实验,利用荧光激发-发射矩阵光谱(EEMs)研究了再悬浮过程中从沉积物中释放出的有色溶解有机物(CDOM)的荧光特征,同时通过与相应站位沉积物间隙水和底层水的对比分析,探讨了河口近岸海域的沉积物再悬浮作用作为水体中溶解有机物来源之一的可能性.结果表明,对给定站位,CDOM相对荧光强度和溶解有机碳(DOC)含量分布变化非常一致,均为间隙水最高,再悬浮次之,底层水最低;站位之间,底层水和再悬浮水样中CDOM相对荧光强度随盐度的降低而增加,从海端向河端增加的趋势明显.EEMs分析表明,各样品中均存在类腐殖质荧光与类蛋白质荧光团,且模拟实验也表明再悬浮作用可释放类腐殖质与类蛋白质荧光物质到底层水中,表明底质再悬浮将是近岸水体中CDOM的一个重要来源.与相应的底层水相比,间隙水的荧光峰(如峰A/C)的位置发生红移.再悬浮样品中EEMs的荧光团同时表现出相应底层水和间隙水的特征,但是荧光峰(峰A和峰C)的最大激发和发射波长更接近底层水中相应荧光团,与间隙水相比,则发生谱峰位置的蓝移.近海端样品中荧光峰M明显,随着盐度的降低,底层水和再悬浮水样的γ(M/C)值逐渐降低,且海源的峰M由海端向河端逐渐消失,表明峰M属于海洋自生来源.本研究区域DOM的荧光指数在1.61～1.93之间,表明近海端样品DOM主要为生物来源,而近河端样品DOM主要为陆源输入,或者为陆源与生物活动共同作用的结果.     

Origin and composition of organic matter in tidal flat sediments from the German Wadden Sea

Two sediment cores of up to 550 cm length from an intertidal flat of the German Wadden Sea near the island of Spiekeroog were investigated for the quantity and composition of fossil organic matter (OM). The lowermost parts of the cores are dominated by grey mud of a salt marsh facies containing mainly terrestrial OM estimated to account for 60–75% of the total OM, based on δ¹³C values and the ratio of short to long chain n-alkanols. The terrigenous origin of the dominant fraction is indicated, among others, by high proportions of C₂₉ sterols and long chain n-alkanes typical of plant waxes. Coarse shell beds overlying the grey mud at 2–2.5 m depth represent a flooding and erosion event possibly related to heavy storm floods in the Middle Ages. Within the intertidal sand-dominated sediments in the upper parts of the cores total organic carbon (TOC) contents are generally low, ranging from 0.1% to 0.5%, and correlate well with the amount of mud fraction (r² 0.90). At the surface, marine OM has not undergone intense diagenetic alteration and so is the dominant fraction. Eroded peat particles are common throughout most of the sequence and values of the Phragmites peat indicator (PPI) > 5 indicate an origin from reed peat due to a high relative abundance of the n-C₂₄ alkane. Changes in the composition of microbial communities over the depth interval investigated are documented by varying compositions of unsaturated fatty acids with 16 and 18 carbons. Eicosapentaenoic acid (EPA) was detected along the entire cores and indicates the presence of EPA-producing bacterial strains.     

Total mercury and methylmercury in sediments near offshore drilling sites in the Gulf of Mexico

Concentrations of total Hg in sediments near six drilling sites in the Gulf of Mexico were elevated well above average background values of 40–80 ng/g. The excess Hg was associated with barite from discharged drilling mud. In contrast with total Hg, concentrations of methylmercury (MeHg) in these sediments did not vary significantly at nearfield (<100 m) versus farfield (>3 km) distances from the drilling sites. Observed variability in concentrations of MeHg were related to local differences in redox state in the top 10 cm of sediment. Low to non-detectable concentrations of MeHg were found in nearfield sediments that were anoxic, highly reducing and contained abundant H₂S. At most drilling sites, nearfield samples with high concentrations of total Hg (>200 ng/g) had similar or lower amounts of MeHg than found at background (farfield) stations. Higher values of MeHg were found in a few nearfield sediments at one site where concentrations of TOC were higher and where sediments were anoxic and moderately reducing. Overall, results from this study support the conclusion that elevated concentrations of MeHg in sediments around drilling sites are not a common phenomenon in the Gulf of Mexico.     

Sulfate reduction and the nature of organic matter in estuarine sediments

The reduction of sulfate by sulfate reducing bacteria in the anoxic zone is an extremely important process during early diagenesis of marine sediments. Our data from Great Bay, NH reinforce the proposal that the rate of sulfate reduction is directly proportional to the reactivity of the organic matter or the amount of readily metabolizable organic matter present in the sediment and, hence, the source of the organic material in the anoxic zone. It appears that organic matter rich in marine organic remains is more easily degraded in the anoxic zone and that sulfate reduction rates can vary considerably in an estuarine system where many types of organic material may be deposited.