Assessment of copper,cadmium and zinc remobilization in Mediterranean marine coastal sediments

The remobilization of copper, cadmium and zinc in sediments of three selected coastal microenvironments of the Aegean Sea (Eastern Mediterranean) is assessed. Various analytical methods and techniques were employed providing concentrations, profiles and forms of metals and organic matter in sediments and pore waters.     

Acetate in recent anoxic sediments: Direct and indirect measurements of concentration and turnover rates

While acetate is generally regarded as an important intermediate in the mineralization of organic matter in anoxic sediment systems, some quantitative studies in marine systems (including our own) have measured acetate oxidation rates in excess of sulphate reduction rates where sulphate is known to be the principal electron acceptor. We revisited Skan Bay, Alaska, where we had previously made such observations, for a reexamination of acetate turnover. Measurements of acetate concentrations, production rate, oxidation rate and sulphate reduction rate as well as bioenergetic considerations led to the conclusion that acetate oxidation rate in 15–18-cm deep sediment is 1·1–1·5 μM h⁻¹. The possibility that previous measurements were high because of a non-citric-acid-cycle pathway of acetate oxidation (suggested by recent laboratory studies) was excluded. It appears that our previous turnover measurements were high mainly because of high acetate concentrations. Procedures used for the isolation of porewater for acetate determination may influence results to an extent not previously recognized.     

The relationship between fatty acid distributions and bacterial respiratory types in contemporary marine sediments

Bacterial communities of different respiratory types were isolated from a marine sediment in a multiple chemostat system in an attempt to obtain bacterial cultures representative of the sediment. The fatty acid distribution of a mixed culture of sulphate-reducing bacteria isolated from this system showed a good correlation with the lipid distribution of the zone of maximum sulphate-reduction activity within the sediment. Both distributions had significant concentrations of C14 : 0, iso and anteiso C15 : 0, C16 : 0, C16 : 1ω7 and C18 : 1ω7. This was in contrast to the lipid profile of Desulfovibrio desulfuricans obtained by batch enrichment, which was dominated by iso C17 : 1ω7 fatty acids and correlated poorly with the sediment. The bacterial community cultured from the sediment was further differentiated according to respiratory types (aerobic, facultative aerobic and facultative anaerobic) by growth in a chemostat under defined conditions. The fatty acid distributions of these communities were sufficiently different to enable the various respiratory types to be recognized by their particular fatty acid composition. Cyclopropyl fatty acids (?17 and ?19) were present in significant levels only in the aerobic bacteria, while the facultative aerobes had significantly higher C18 : 1ω7 than the other cultures and the facultative anaerobic community was the only culture to have significant amounts of C12 : 0. The fatty acid distribution of Loch Eil sediment over the range C12-19 seemed to be predominantly of bacterial origin and were relatively abundant to a depth of 6 cm. The concentration of cyclopropyl fatty acids was highest in the oxidized surface sediments and decreased with depth as anaerobic conditions began to dominate, indicating that these fatty acids may only be indicative of aerobic sedimentary bacteria. In contrast to the fatty acids characteristic of bacteria, those fatty acids in the range C20-30 attributed to a terrestrial input were found in relatively constant concentrations over the whole 0–12 cm depth profile.     

Behaviour of copper,zinc, iron and manganese during experimental resuspension and reoxidation of polluted anoxic sediments

Samples of anoxic intertidal sediments from the Mersey Estuary, north-west England, have been used in laboratory experiments to determine the rates and extents of metal (Cu, Zn, Fe, Mn) releases to solution under conditions of controlled resuspension and reoxidation. An experimental system for the study of sediment-water interactions at various temperatures, salinities, pHs and oxygen concentrations is described. The results indicate rapid initial losses of Fe and Mn from sediment but not Cu and Zn with longer term readsorption of Fe and Mn to give partitioning between the aqueous/ sediment phases for all four metals which is similar to that under the initial anoxic conditions. Cu and Zn show small, but measurable, net losses from the aqueous phase to the reoxidized sediment. Salinity variations exert little influence on the processes observed, but increasing temperature produces increased Cu, Zn and Mn in the dissolved fraction at equilibrium conditions. Exchanges of Cu and Zn between the sediment/water phases are rather insensitive to pH or oxygen concentration, but Fe and Mn do respond to increasing pH which suppresses their initial release on oxidation. Low oxygen concentrations can result in a slow but significant release of Fe. In relation to trace metal pollution in estuaries and biological availability, the results suggest that the resuspension and oxidation of polluted anoxic sediments is not an important process because of scavenging of soluble metals on to the resuspended material.     

The distribution and flux of particulate matter in the Bideford River Estuary,Prince Edward Island,Canada

The temporal and spatial distribution of total and organic particulate matter is investigated in the Bideford River estuary. Particulate matter is homogenously distributed in both the water column and the surface sediment, due to high rates of resuspension and lateral transport. The measured mean sedimentation rate for the estuary is 183·5 g of particulate matter m^?2 day^?1, of which more than half is due to resuspension.The surface sediment of the estuary is quantitatively the dominant reservoir of organic matter, with an average of 902·5 g of particulate organic carbon (POC) m^?2 and 119·5 g of particulate organic nitrogen (PON) m^?2. Per unit surface area, the sediment contains 450 times more POC and 400 times more PON than the water column. Terrestrial erosion contributes high levels of particulate matter, both organic and inorganic, to the estuary from the surrounding watershed. Low rates of sediment export from the estuary result in the accumulation of the terrigenous material. The allochthonous input of terrigenous organic matter masks any relationship between the indigenous plant biomass and the organic matter.In the water column, a direct correlation exists between the organic matter, i.e. POC and PON, concentration and the phytoplankton biomass as measured by the plant pigments. Resuspension is responsible for the residual organic matter in the water column unaccounted for by the phytoplankton biomass.The particulate content of the water column and the surface sediment of the estuary is compared to that of the adjacent bay. Water-borne particulate matter is exported from the estuary to the bay, so that no significant differences in concentration are noted. The estuarine sediment, however, is five to six times richer in organic and silt-clay content than the bay sediment. Since sediment flux out of the estuary is restricted, the allochthonous contribution of terrigenous particulate matter to the bay sediment is minor, and the organic content of the bay sediment is directly correlated to the autochthonous plant biomass.     

Fluxes of organic carbon in a fjord on the west coast of Ireland

The supply of particulate organic carbon (POC) via freshwater influx, and its exchange with the open sea, were estimated for a fjord-like coastal inlet (Killary Harbour, Ireland) during 1981. Biological production and destruction of organic matter within the inlet were also studied. POC levels in rivers feeding the system were correlated with rainfall. C : N ratios suggested an increased proportion of POC of terrestrial origin at stations influenced by freshwater inflow, and throughout the fjord in the non-productive season.A tentative annual carbon budget is presented.     

Trace metal composition of and accumulation rates of sediments in the Upper Gulf of Thailand

Sediment cores and grab samples were collected in the Upper Gulf of Thailand to determine sedimentation rates and to determine if metal concentrations reflect anthropogenic inputs.Accumulation rates of sediments in the Upper Gulf measured using the ²¹⁰Pb method, appear to vary from ca. 4 to 11 mm yr^?1. Sediment budgets suggest that little of the sediment delivered to the Upper Gulf by the major rivers is ultimately transported to the Lower Gulf. Metal concentrations in Upper Gulf sediments appear to be dominantly controlled by natural inputs.     

The long-term effects of crude oil on microbial processes in subarctic marine sediments

Subarctic marine sediments were exposed to fresh and ‘weathered’ crude oil from Cook Inlet, Alaska. The crude oil was thoroughly mixed with the sediment at various concentrations and some of the oil-sediment mixtures were placed on top of unamended sediments. Both sediments with added oil and those overlain by oiled sediments were investigated. These sediments were placed either in trays or aquaria. The trays were incubated in situ near the site from which the sediments were originally collected. The aquaria were maintained at simulated in situ conditions by maintaining a continuous flow of fresh seawater through them. The sediments were exposed to crude oil for periods up to 1.5 years. Sediments exposed to 50‰ fresh crude oil showed significant decreases in nitrogen fixation and denitrification rates and redox potentials. Also observed were increases in CO₂ production rates and methane concentrations. These same changes were observed in sediments exposed to 1‰. When ‘weathered’ crude oil was added to the sediments, the same changes were observed except there was no reduction in nitrogen fixation activity. In most cases, the observed effects were less marked when the sediments were amended with ‘weathered’ crude oil than with the same concentration of fresh crude oil. Untreated sediments that were overlain with treated sediments showed the same changes as those sediments that were thoroughly mixed with crude oil. The presence of fresh crude oil at 50‰ essentially eliminated burrowing activity of the benthic infauna. Under these conditions, there was an accumulation of detritus particles on the oiled sediments that was not present in the untreated controls.     

Chlorinated hydrocarbons in the seawater and surface sediments of Blanca Bay,Argentina

In order to characterize our study area and to provide reference values to be used in the future to measure the changes produced by an increase in contamination, the concentrations of chlorinated hydrocarbons have been investigated in fifty-one samples of seawater, taken at four different depths: air-sea interface, surface, one metre and bottom waters, and in twenty-three samples of surface sediments from Blanca Bay, Argentina. Of eleven organochlorine compounds we were looking for (α BHC, lindane, heptachlor, δ BHC. aldrin, heptachlor epoxide, dieldrin, o-p′DDD, p-p′DDD, o-p′DDT and p-p′DDT), seven could be detected in seawater and three in surface sediments with the following mean concentrations: α-BHC=48·2 ng l^?1; lindane=54·2 ng l^?1; heptachlor=45·0 ng l^?1; δ BHC=12·5 ng l^?1; aldrin=61·8 ng l^?1 and ΣDDT=67·0 ng l^?1; and δ BHC=3·2 ng g^?1; lindane=4·2 ng g^?1 and heptachlor=1·0 ng g^?1 for seawater, regarding the surface waters, and sediment samples, respectively.Concentration factors among the different water layers were also studied to see if there was any correlation between chlorinated hydrocarbon contents and the water depths from which the samples were taken. As a mean value, the air-sea interface water contains 18 times more of these compounds than that of the water near the bottom. A comparison of the values corresponding to seawater and surface sediments from our study area with those levels measured in samples from other geographic locations is also presented.With the purpose to detect a relationship between chlorinated hydrocarbon concentrations and the contents of particulate matter (PM) on the one hand, and particulate organic material (POM) on the other hand, four groups of samples containing different amounts of PM and POM, respectively were formed. From a comparison of the results obtained, lindane, heptachlor and δ BHC showed a tendency to lower concentrations in those samples containing little PM whereas α BHC and aldrin remained without important changes. No significant correlation was found between organochlorine levels and contents of POM.     

Behaviour of metallic and radioactive elements in lagoonal sediments: the example of the Canet-St Nazaire Pond (Mediterranean coast)

The behaviour of Ca, Mg, Na, K, Fe, Mn, Zn and radionuclides (U, Th, Pb, Ra) was studied in water, suspensions and sediments of an euxinic lagoonal environment of the French Mediterranean coast. The dynamic of these elements at the sediment-water interface is considered particularly in relation to the redox conditions, the nature of inorganic and organic supports and the sedimentation rate.     

Fatty acids in recent sediments in the St. Lawrence estuary

Surface sediments along the Rimouski section in the St. Lawrence estuary were sampled at the surface and at 10 cm depth. Fatty acids were extracted and analysed. Saturated and unsaturated fatty acid contents at the two depths vary with the nature of the sediments. The clay sediments rich in organic matter contain more fatty acids than the corresponding sand or gravel. Unsaturated fatty acids were more abundant in the surface sediments. Some iso- and anteiso-odd carbon fatty acids were detected in the sediments; these acids could indicate a microbial activity. Correlation is made with the fatty acid contents of the water column together with the surface microlayer of the estuarine water.     

Metal binding by humic acids in recent sediments from the SW Iberian coastal area

The concentrations of Cu, Zn, Cr, Ni, Pb, As, Mn and Co were determined by Inductively Coupled Plasma–Mass Spectrometry both in recent sediments from different locations of the Huelva littoral (SW Iberian Peninsula) and in their humic acid (HA) fractions in order to evaluate distribution and binding capacity of those trace elements to HAs. In addition, elemental composition (C, N, S) and δ¹³C values were determined to appraise the sources of organic matter in the area. This study involved the comparison of selected samples taken from different environments including the estuary of the Guadiana River, the main fluvial system of the region, the Tinto and Odiel estuary system and the proximal shelf. Significant positive correlations were found among Cu, Zn, As and Pb in bulk sediments, suggesting a common origin of all of those elements: the mining activities and pyrite deposits located hinterland. On the other hand, results for Cr, Co and Ni pointed to the basic rocks from the low basin of the Guadiana River as their main source. Elemental (C, N) and isotopic (δ¹³C) composition of sediments indicated a significant contribution of autochthonous plankton in coastal shelf sediments, whereas estuarine and riverine sediments showed a major contribution of terrestrial biomass. Geochemical values for their corresponding HAs suggested a greater terrestrial contribution in the sedimentary OM of the coastal shelf sediments than in bulk sediments, which evidenced the influence of coastal currents and sediment fluxes. Humic acids sequester considerable amounts of Cu and Zn contributing to reduce the bioavailability of these contaminants.     

The vertical attenuation of light in Charlotte Harbor, a shallow, subtropical estuary, south-western Florida

The relative contribution of different components to the attenuation of photosynthetically active radiation was determined in the Charlotte Harbor estuarine system based on laboratory and in situ measurements. Agreement between laboratory and in situ measurements of the attenuation coefficient (k_t) was good (r² = 0·92). For all in situ measurements (n = 100), suspended, non-chlorophyll matter accounted for an average of 72% of k_t, dissolved matter accounted for 21%, suspended chlorophyll for 4%, and water for the remaining 3%.For individual determinations, suspended non-chlorophyll matter, dissolved matter, suspended chlorophyll, and water, each accounted for as much as 99%, 79%, 21%, and 18% of k_t. Attenuation by suspended matter was greatest near the mouth of the northern tidal rivers and was variable over the rest of the estuarine system. Attenuation by dissolved matter was greatest in the brackish tidal rivers and decreased with increasing salinity. Attenuation due to dissolved matter was positively correlated with water color. The source of the color was basin runoff. Wavelength transmittance changed along the salinity gradient. Maximum transmittance shifted from 500 to 600 nm in gulf waters to 650 to 700 nm in colored, brackish waters. Dissolved matter was primarily responsible for the large attenuation at short wavelengths (400–500 nm).     

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。     

Sources and timing of trace metal contamination to sediments in remote sealochs,N.W. Scotland

Sediment cores from a transect of sealochs, Etive, Sunart, Nevis, Duich, Broom and Torridon in N.W. Scotland were analysed for the trace metals lead, copper, and zinc. In addition, sediment cores from the Clyde Sea Basin (Loch Fyne, the Gareloch, Clyde dumpsite) and from the Irish and Celtic Seas were analysed as possible source areas for contaminated particles. The sediment cores were dated using excess ²¹⁰Pb and ¹³⁷Cs, and Al normalisation was used to correct for sediment compositional effects. All cores showed increased concentrations of all trace metals (and M/Al) towards the surface, with a maximum of 280–500% above background being observed in Loch Etive. Only cores from Duich and Torridon (Zn/Al and Pb/Al) and Etive (Zn/Al) did not continue to show an increase in trace metals to the uppermost samples. The burden of atmospherically derived trace metals accumulated over the past 100 years was compared with similar published burdens from a series of freshwater lochs adjacent to the sealochs. Plots of excess ²¹⁰Pb (used to correct for sediment focusing) against atmospherically derived Pb showed a series of linear relationships of systematically decreasing gradient towards the north-west, away from potential urban sources of lead. It was calculated that 49% (15–77%) of the Pb but only 3% (1–4%) of the Zn and 2% (0–3%) of the Cu reached the sealochs from atmospheric sources. The remaining trace metals deposited in the sealochs came from marine particles. Using trace metal ratios as an indicator of pollutant provenance, it was shown that the trace metals came predominantly from the Irish Sea. There was no evidence of trace metals derived from the Firth of Clyde basin. It was concluded that trace metal contamination from the Clyde and the surrounding industrialised urban area was mainly deposited in the estuary and the Clyde Sea basin with its adjoining sealochs, such as the Gareloch and Loch Fyne.     

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.