Potential links between Baltic Sea submarine terraces and groundwater seeping

Submarine groundwater discharge (SGD) influences ocean chemistry, circulation, and the spreading of nutrients and pollutants; it also shapes sea floor morphology. In the Baltic Sea, SGD was linked to the development of terraces and semicircular depressions mapped in an area of the southern Stockholm archipelago, Sweden, in the 1990s. We mapped additional parts of the Stockholm archipelago, areas in Blekinge, southern Sweden, and southern Finland using high-resolution multibeam sonars and sub-bottom profilers to investigate if the sea floor morphological features discovered in the 1990s are widespread and to further address the hypothesis linking their formation to SGD. Sediment coring and sea floor photography conducted with a remotely operated vehicle (ROV) and divers add additional information to the geophysical mapping results. We find that terraces, with general bathymetric expressions of about 1 m and lateral extents of sometimes > 100 m, are widespread in the surveyed areas of the Baltic Sea and are consistently formed in glacial clay. Semicircular depressions, however, are only found in a limited part of a surveyed area east of the island of Asko, southern Stockholm archipelago. While submarine terraces can be produced by several processes, we interpret our results to be in support of the basic hypothesis of terrace formation initially proposed in the 1990s; i.e. groundwater flows through siltier, more permeable layers in glacial clay to discharge at the sea floor, leading to the formation of a sharp terrace when the clay layers above seepage zones are undermined enough to collapse. By linking the terraces to a specific geologic setting, our study further refines the formation hypothesis and thereby forms the foundation for a future assessment of SGD in the Baltic Sea that may use marine geological mapping as a starting point. We propose that SGD through the submarine sea floor terraces is plausible and could be intermittent and linked to periods of higher groundwater levels, implying that to quantify the contribution of freshwater to the Baltic Sea through this potential mechanism, more complex hydrogeological studies are required.Peer reviewe

An enormous amorphous silica stock in boreal wetlands

We investigated amorphous Si (ASi) in a boreal wetland in northern Sweden. We found enormous stocks of ASi in the upper soil layers (up to 11% of dry weight), in the form of diatom frustules and plant ASi. A consistent exponential decrease in ASi concentrations was observed with increasing depth in the soil profile. An inverse modeling approach shows that vegetation takes up a substantial part of weathered dissolved Si (DSi). Concurrent analysis of N and C indicates a faster turnover in and a higher leakage from the ASi pool. The magnitude of the biological buffering we observed is unprecedented and supports the emerging paradigm of the importance of biological uptake of DSi governing the export of DSi from terrestrial ecosystems. Our results complicate current models of silicate transport, highlighting the necessity to incorporate ecosystem biological buffering in our concept of Si biogeochemistry

Anthropogenic Inputs of Terrestrial Organic Matter Influence Carbon Loading and Methanogenesis in Coastal Baltic Sea Sediments

Coastal regions globally have experienced widespread anthropogenic eutrophication in recent decades. Loading of autochthonous carbon to coastal sediments enhances the demand for electron acceptors for microbial remineralization, often leading to rearrangement of the sediment diagenetic zonation and potentially enhancing fluxes of methane and hydrogen sulfide from the seafloor. However, the role of anthropogenic inputs of terrestrial organic matter (OMterr.) in modulating diagenesis in coastal sediments is often overlooked, despite being of potential importance in regions of land-use and industrial change. Here we present a dated 4-m sediment and porewater geochemistry record from a eutrophic coastal location in the northern Baltic Sea, to investigate sources of recent carbon loading and their impact on modern diagenetic processes. Based on an end-member mixing model of sediment N/C ratios, we observe that a significant fraction of the late-20th century carbon loading at this location was contributed by OMterr.. Furthermore, analysis of lignin in this material shows depleted ratios of syringyl/vanillyl (S/V) and cinnamyl/vanillyl (C/V) phenols, indicative of enhanced inputs of woody gymnosperm tissue likely from forest industries. The rapid loading of organic matter from combined terrestrial and autochthonous sources during the late 20th century has stimulated methanogenesis in the sediment column, and shoaled the sulfate-methane transition zone (SMTZ) to a depth of 5-20 cm. Optical parameters of colored dissolved organic matter confirm that OMterr. is actively degrading in the methanogenic layer, implying a role for this material in diagenetic processes. Porewater CH4, SO4 (2-) delta C-13-DIC, and n-ary sumation S2- data suggest that the modern SMTZ is a broad zone in which organoclastic sulfate reduction, methanogenesis and anaerobic oxidation of methane (AOM) co-occur. However, fluxes of CH4 and SO4 (2-) show that rates of these processes are similar to other marine locations with a comparably shallow SMTZ. We suggest that the shallow depth of the modern SMTZ is the principal reason for high observed diffusive and ebullitive methane fluxes from sediments in this area. Our results highlight that anthropogenic activities lead to multiple pathways of carbon loading to coastal sediments, and that forest industry impacts on sedimentation in the northern Baltic Sea may be more widespread than previously acknowledged.Peer reviewe

Ice export from the Laptev and East Siberian Sea derived from delta O-18 values

Ice export from the vast Arctic Siberian shelf is calculated using O-18 values and salinity data for water samples collected during the International Siberian Shelf Study between August and September 2008 (ISSS-08). The samples represent a wide range of salinities and O-18 values due to river water inputs and sea ice removal. We estimate the fraction of water that has been removed as ice by interpreting observed O-18 values and salinities as a result of mixing between river water and sea water end-members as well as to fractional ice removal. This method does not assume an ice end-member of fixed composition, which is especially important when applied on samples with large differences in salinity. The results show that there is net transport of ice from both the Laptev and the Eastern Siberian Seas, and in total 3000 km(3) of sea ice is exported from the shelf. The annual total export of ice from the entire region, calculated from the residence time of water on the shelf, is estimated to be 860 km(3) yr(-1). Thus, changes in ice production on the shelf may have great impact on sea ice export from the Arctic Ocean

Non-Redfieldian Dynamics Explain Seasonal pCO(2) Drawdown in the Gulf of Bothnia

High inputs of nutrients and organic matter make coastal seas places of intense air-sea CO2 exchange. Due to their complexity, the role of coastal seas in the global air-sea CO2 exchange is, however, still uncertain. Here, we investigate the role of phytoplankton stoichiometric flexibility and extracellular DOC production for the seasonal nutrient and CO2 partial pressure (pCO(2)) dynamics in the Gulf of Bothnia, Northern Baltic Sea. A 3-D ocean biogeochemical-physical model with variable phytoplankton stoichiometry is for the first time implemented in the area and validated against observations. By simulating non-Redfieldian internal phytoplankton stoichiometry, and a relatively large production of extracellular dissolved organic carbon (DOC), the model adequately reproduces observed seasonal cycles in macronutrients and pCO(2). The uptake of atmospheric CO2 is underestimated by 50% if instead using the Redfield ratio to determine the carbon assimilation, as in other Baltic Sea models currently in use. The model further suggests, based on the observed drawdown of pCO(2), that observational estimates of organic carbon production in the Gulf of Bothnia, derived with the 14C method, may be heavily underestimated. We conclude that stoichiometric variability and uncoupling of carbon and nutrient assimilation have to be considered in order to better understand the carbon cycle in coastal seas.Peer reviewe

Using ocean quahog (Arctica islandica) shells to reconstruct palaeoenvironment in A-resund, Kattegat and Skagerrak, Sweden

Shells of Arctica islandica collected between 1884 and 2004 from A-resund, Kattegat and Skagerrak (Swedish West Coast) were used to monitor local climate variations and the influence of human activities on the local environment. For this purpose, we analysed the growth, structure and chemical composition of these shells and compared them with shells collected from Kiel Bay, Norway and Iceland. The growth rate of the studied shells registers an NAO periodicity of ca 8 years. However, the observed signal is weak because of other environmental interferences that are either of natural or anthropogenic origin. For example, the oxygen isotope ratios show temperature fluctuation, but also the influx of low salinity water. Higher contents of S, N, Cu, Zn, As, Cd and P in shell portions formed during the last century are related to human activities such as mining and industrial development. Our study indicates that in order to use Arctica shells as archives of climate change it is necessary to study the full range of environmental data that is recorded in the shells by using a multi element and isotope approach in combination with different analytical techniques including investigation of growth rates and shell structure

Past, present and future state of the biogeochemical Si cycle in the Baltic Sea

The Baltic Sea is one of many aquatic ecosystems that show long-term declines in dissolved silicate (DSi) concentrations due to anthropogenic alteration of the biogeochemical Si cycle. Reductions in DSi in aquatic ecosystems have been coupled to hydrological regulation reducing inputs, but also with eutrophication, although the relative significance of both processes remains unknown for the observed reductions in DSi concentrations. Here we combine present and historical data on water column DSi concentrations, together with estimates of present river DSi loads to the Baltic, the load prior to damming together with estimates of the long-term accumulation of BSi in sediments. In addition, a model has been used to evaluate the past, present and future state of the biogeochemical Si cycle in the Baltic Sea. The present day DSi load to the Baltic Sea is 855 ktons y(-1). Hydrological regulation and eutrophication of inland waters can account for a reduction of 420 ktons y(-1) less riverine DSi entering the Baltic Sea today. Using published data on basin-wide accumulation rates we estimate that 1074 ktons y(-1) of biogenic silica (BSi) is accumulating in the sediments, which is 36% higher than earlier estimates from the literature (791 ktons y(-1)). The difference is largely due to the high reported sedimentation rates in the Bothnian Sea and the Bothnian Bay. Using river DSi loads and estimated BSi accumulation, our model was not able to estimate water column DSi concentrations as burial estimates exceeded DSi inputs. The model was then used to estimate the BSi burial from measured DSi concentrations and DSj load. The model estimate for the total burial of BSi in all three basins was 620 ktons y(-1), 74% less than estimated from sedimentation rates and sediment BSi concentrations. The model predicted 20% less BSi accumulation in the Baltic Proper and 10% less in the Bothnian Bay than estimated, but with significantly less BSi accumulation in the Bothnian Sea by a factor of 3. The model suggests there is an overestimation of basin-wide sedimentation rates in the Bothnian Bay and the Bothnian Sea. In the Baltic Proper, modelling shows that historical DSi concentrations were 2.6 times higher at the turn of the last century (ca. 1900) than at present. Although the DSi decrease has leveled out and at present there are only restricted areas of the Baltic Sea with limiting DSi concentrations, further declines in DSi concentrations will lead to widespread DSi limitation of diatoms with severe implications for the food web. (C) 2008 Elsevier B.V. All rights reserved

Hydrogeochemical controls on the mobility of arsenic, fluoride and other geogenic co-contaminants in the shallow aquifers of northeastern La Pampa Province in Argentina

Elevated Arsenic (As) and Fluoride (F) concentrations in groundwater have been studied in the shallow aquifers of northeastern of La Pampa province, in the Chaco-Pampean plain, Argentina. The source of As and co-contaminants is mainly geogenic, from the weathering of volcanic ash and loess (rhyolitic glass) that erupted from the Andean volcanic range. In this study we have assessed the groundwater quality in two semi-arid areas of La Pampa. We have also identified the spatial distribution of As and co-contaminants in groundwater and determined the major factors controlling the mobilization of As in the shallow aquifers. The groundwater samples were circum-neutral to alkaline (7.4 to 9.2), oxidizing (Eh ~0.24 V) and characterized by high salinity (EC = 456–11,400 μS/cm) and Na+–HCO3– water types in recharge areas. Carbonate concretions (“tosca”) were abundant in the upper layers of the shallow aquifer. The concentration of total As (5.6 to 535 μg/L) and F (0.5 to 14.2 mg/L) were heterogeneous and exceeded the recommended WHO Guidelines and the Argentine Standards for drinking water. The predominant As species were arsenate As(V) oxyanions, determined by thermodynamic calculations. Arsenic was positively correlated with bicarbonate (HCO3−), fluoride (F), boron (B) and vanadium (V), but negatively correlated with iron (Fe), aluminium (Al), and manganese (Mn), which were present in low concentrations. The highest amount of As in sediments was from the surface of the dry lake. The mechanisms for As mobilization are associated with multiple factors: geochemical reactions, hydrogeological characteristics of the local aquifer and climatic factors. Desorption of As(V) at high pH, and ion competition for adsorption sites are considered the principal mechanisms for As mobilization in the shallow aquifers. In addition, the long-term consumption of the groundwater could pose a threat for the health of the local community and low cost remediation techniques are required to improve the drinking water quality