Trace element diagenesis in pyrite-rich sediments of the Achterwasser lagoon, SW Baltic Sea

The early diagenesis of trace elements (V, Cr, Co, Cu, Zn, As, Cd, Ba, U) in anoxic sediments of the Achterwasser, a shallow lagoon in the non-tidal Oder estuary in the Baltic Sea, was investigated in the context of pyrite formation. The dissolved major redox parameters show a two-tier distribution with transient signals in the occasionally re-suspended fluid mud layer (FM) and a permanently established diagenetic sequence in the sediment below. Intense microbial respiration leads to rapid depletion of O₂ within the uppermost mm of the FM. The reduction zones of Mn, Fe and sulfate overlap in the FM and in the permanently anoxic sediment section which appears to be a typical feature of estuarine sediments, under low-sulfate conditions. Degrees of pyritization (DOP) range from 50% in the FM to remarkably high values > 90% at 50 cm depth. Pyrite formation at the sediment surface is attributed to the reaction of Fe-monosulfides with intermediate sulfur species via the polysulfide pathway. By contrast, intense pyritization in the permanently anoxic sediment below is attributed to mineral growth via adsorption of aqueous Fe-sulfide complexes onto pyrite crystals which had originally formed in the surface layer.The studied trace elements show differential behavior patterns which are closely coupled to the diagenetic processes described above: (i) Zn, Cu and Cd are liberated from organic matter in the thin oxic layer of the sediment and diffuse both upwards across the sediment/water boundary and downwards to be trapped as monosulfides, (ii) V, Cr, Co and As are released during reductive dissolution of Mn- and Fe-oxyhydroxides, (iii) U removal from pore water occurs concomitantly to Fe reduction in the FM and is attributed to reduction of U(VI) to U(IV), (iv) the Ba distribution is controlled by reductive dissolution of authigenic barite in the sulfate reduction zone coupled with upward diffusion and re-precipitation. The incorporation of trace elements into pyrite is most intense for Co, Mn and As, intermediate for Cu and Cr and little to negligible for U, Zn, Cd, V and Ba. The observed trend is largely in agreement with previous studies and may be explained with differing rates for ligand exchange. Slow and fast ligand exchange and thus precipitation kinetics are also displayed by downcore increasing (Mn, Cr, Co and As) or constantly low (Zn, Cu, Cd) pore water concentrations. The downward increasing degrees of trace metal pyritization (DTMP) for Co, Cu, Zn and As are, in analogy to pyrite growth, assigned to adsorption of sulfide complexes or As oxyanions onto preexisting pyrite minerals.     

Budgets of Mn,Cd and Cu in the macrotidal Gironde estuary (SW France)

The behavior and budget of Mn, Cd and Cu in the Gironde estuary were investigated through data from both the water column (WC) and sediment depth profiles. In the estuarine freshwater reaches, Mn and Cd removal from and Cu addition to the dissolved phase occurs with a magnitude equivalent to 10%, 30% and 25% of their respective annual fluvial gross dissolved input, respectively. In the saline estuary, diffusive benthic outflow is the main source of dissolved Mn (74% of the total gross dissolved input within the estuary) to the WC. In contrast, Cd (96%) and Cu (89%) are mainly released into the dissolved phase of the WC from fluvial, estuarine and dredging-related particles through complexation (Cd) and organic carbon mineralization (Cu). Anthropogenic activities (sediment dredging) induce pore water inputs, particulate sulfide oxidation and sediment resuspension, significantly contributing to the metal budget of the WC. The related amounts of metals released could be equivalent to 20–50% (Cd) and up to 70% (Cu) of their respective net dissolved addition. Mass balances suggest that a large part of the metals previously released into the dissolved phase from processes within the estuary are removed by suspended particles due to (co-)precipitation of Fe/Mn (oxy)hydroxides and scavenging on autochthonous organic matter. On an annual basis, the Gironde estuary acts as a net sink of dissolved Mn, removing 60% of the dissolved fluvial inputs, and as a net source of dissolved Cd and Cu, contributing ∼ 85% and 20–45% to the dissolved Cd and Cu fluxes to the ocean.     

福建罗源湾海滩互花米草盐沼中18种金属元素的分布

本文对福建罗源湾可湖海滩互花米草盐沼中的18种金属进行了测试,结果表明,罗源湾可湖海滩的环境质量基本是好的,并探讨了开发利用互花米草的新途径。     

Size distribution of colloidal trace metals and organic carbon during a coastal bloom in the Baltic Sea

The physico-chemical speciation of organic carbon and selected metals was measured during a coastal bloom in Ekhagen Bay, Baltic Sea, using ultrafiltration.One important objective with the study was to see if any depletion of trace metals could be measured in the directly bioavailable fraction (<1000 Da, the soluble low molecular weight fraction, LMW) during a plankton bloom. Filters with five different cut-offs were used (1 kD (1000 Da), 5 kD, 10 kD, 100 kD and 0.22 μm) in order to delineate the size distribution of colloidal organic carbon (COC) and trace metals.During the bloom in May, LMW Al, Co, Cu, Mn and Ni concentrations decreased although the colloidal and particulate concentrations were relatively high. Data show that desorption of colloidal and particulate bound trace metals to the LMW fraction was slower than the process depleting the LMW fraction.Estimates of the maximum active uptake of Cu, Ni and Mn by the phytoplankton, and the loss of non-bioactive Al from the LMW fraction, indicate that processes other than active uptake by phytoplankton must contribute to the observed depletion of trace metals in the LMW fraction. Hence, in order to estimate the bioavailable pool of trace metals for plankton during bloom conditions, these other processes must be understood and quantified.Transparent Exopolymeric Particles (TEP, reflecting sugar-rich phytoplankton exudates) increased around eight times during the plankton bloom. We hypothesize that the formation of TEP is a process that might be important for the transfer of trace metals from the LMW to the particulate fraction during the phytoplankton bloom, but the significance of TEP for this depletion in Baltic Sea surface water remains to be shown.     

Dissolved titanium distributions in the Mid-Atlantic Bight

Although titanium is abundant in Earth's crust, its sources and distribution in the ocean are poorly understood. To elucidate its behavior, distributions of dissolved (< 0.2 μm) Ti were determined in surface waters and vertical profiles from the Mid-Atlantic Bight (MAB). Concentrations of Ti decreased from 390 pM at the Delaware Bay mouth to < 100 pM across the Delaware continental shelf. In vertical profiles, small increases in bottom waters suggest a possible flux of Ti from shelf sediments, consistent with previous reports of pore water enrichments of dissolved Ti in MAB sediments. Concentrations in surface waters of the outer shelf and slope ranged between 30 and 140 pM, with most values below 90 pM. Concentrations in a 1000 m vertical profile in the eastern Gulf Stream ranged between 110 and 280 pM, and showed a variable distribution attributed to the mixing of water masses in the outer MAB. A simple model of Ti sources to the MAB suggests that atmospheric deposition of dissolved Ti is comparable to net riverine contributions and therefore must be considered in applications of Ti as a tracer of oceanographic processes.     

Neoproterozoic trace fossils vs. microbial mat structures: Examples from the Tandilia Belt of Argentina

The Tandilia Belt in northeast Argentina includes a Neoproterozoic sequence of sediments (Sierras Bayas Group), in which the Cerro Largo Formation, ca. 750 Ma in age, forms a siliciclastic, shallowing upward succession of subtidal nearshore to tidal flat deposits. Trace fossils Palaeophycus isp. and Didymaulichnus isp. have been described from the upper part of this succession. Specific sedimentary structures consisting of round-crested bulges, arranged in a reticulate pattern, and networks of curved cracks are associated with the trace fossils. These structures are considered to be related to epibenthic microbial mats that once colonized the sediment surface. They reflect stages of mat growth and mat destruction, if compared to analogous structures in modern cyanobacterial mats of peritidal, siliciclastic depositional systems. Also the trace fossils are interpreted as mat-related structures, partly forming components of networks of shrinkage cracks, partly representing the upturned and involute margins of shrinkage cracks or circular openings in desiccating and shrinking, thin microbial mats.

The definition of Didymaulichnus miettensis Young as a Terminal Proterozoic trace fossil is questioned, and it may be considered to interpret the ‘bilobate’ structure as the upturned, opposite margins of microbial shrinkage cracks which have been brought back into contact by compaction after burial.     

Biological and Geochemical Record of Anthropogenic Impacts in Recent Sediments from Lake Pupuke, Auckland City, New Zealand

Frozen sediment cores from Lake Pupuke in Auckland City, New Zealand, contain a high resolution decadal to annual scale record of changing lake paleoenvironments and geochemistry that reflects changing landuse and hydrology in the catchment over the past c. 190 years. A reliable chronology is available from AMS ¹⁴C and ²¹⁰Pb dating of the sediments, with the timing of the older part of the record supported by the first appearance of pollen of introduced Pinus and Plantago lanceolata associated with European settlement of Auckland in the early 1840s. Diatom stratigraphy, sediment elemental and carbon isotope geochemistry reflect changes in sediment sources and lake conditions commensurate with European development of the Lake Pupuke catchment, in particular enhanced algal productivity controlled by the influx of nutrients after c. 1920 AD. Attempts to prevent nuisance algal blooms in 1933, 1934 and 1939 using CuSO₄ addition produced Cu spikes in the sediment that allowed confirmation of the accuracy of the ²¹⁰Pb chronology. Hence, the elemental and isotopic composition of the Lake Pupuke sediments reflect the timing of significant anthropogenic activities, rather than climatic variations, that have occurred within the watershed over the past c. 190 years. The comparison of records of land use change in the catchment with the multi-proxy record of changes in the sediments usually allowed unambiguous identification of the signatures of change and their causes.     

Dissolved trace elements in river water: spatial distribution and the influencing factor, a study for the Pearl River Delta Economic Zone, China

Twenty-nine water samples were collected from different river channels of the Pearl River Delta Economic Zone, China. An inductively coupled plasma-mass spectromonitor (ICP-MS) was used to measure concentrations of the trace elements in these samples. The results suggest that the average concentrations of rare earth elements in river water show an increasing trend from the West River, the North River, the rivers of the Pearl River Delta, and the Shenzhen River to the East River. Relatively high concentrations of heavy metals appear in the East River, the rivers of the Pearl River Delta and the Shenzhen River, while the West River and the North River have relatively low heavy metal concentrations. Trace element concentrations in samples collected near urban or industrial areas are much higher than those of samples collected from distant areas, away from urban and industrial areas. After natural conditions, human activities have significant influence on the trace element concentrations in river water. This trace element concentration’s spatial distribution in the river water from the Pearl River Delta Economic Zone is actually an integrated effect of natural conditions and human activity.     

Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

追踪法点位探测及其应用

窗口检索是许多信息系统的基本功能之一,包括单窗口检索和多窗口检索。多窗口检索就是判断点状日标位于哪个多边形内,即“点位探测”。在本文介绍了追踪法点位探测的基本思想和方法,并把这一思想引入矢量多边形叠置运算中,有效地提高了矢量叠置的求交效率。