Serpentinization history of the Río Guanajibo serpentinite body,Puerto Rico

The Río Guanajibo serpentinite body (RGSB) near Mayagüez, Puerto Rico, is part of an ophiolite mélange thrust in an oceanic convergent zone. The aim of this study was to characterize the extent and chronology of serpentinization within this peridotite mass. Mineralogy, microstructures, and veining episodes within the RGSB were characterized using optical microscopy, x-ray diffraction (XRD), scanning electron microscopy (SEM), and structural analyses. This study identified, for the first time, all three serpentine polymorphs (i.e., antigorite, chrysotile, lizardite) in serpentinite samples collected from Puerto Rico. Lizardite, the initial serpentine mineral formed from widespread hydration of olivine, was found throughout serpentinite samples. Chrysotile was the most abundant polymorph observed in sheared serpentinite samples, consistent with conditions favoring low fluid to rock ratios, supersaturation and abundant porosity. Antigorite was observed as a replacement texture in serpentinites that were not exposed to greenschist facies metamorphic conditions, and were frequently found in veins with a shear component. The results indicate that metamorphic conditions do not exclusively dictate polymorph formation.The mineralogy and textures observed within the different vein generations reflect the formation conditions, and deformational mechanisms, that occurred during the serpentinization process; six veining episodes (V1 – V6) were identified and grouped into four stages of serpentinization. Stage one (V1 and V2 type veins) represents the earliest stages of serpentinization and was characterized by microscopic fracture networks that formed as a result of cracking during the initial hydration of olivine under low water/rock ratios. During stage two (V3 and V4 type veins), fibrous crack - seal veins formed to accommodate continued volume expansion, via incremental fracture openings, caused by continued hydration of olivine. The ascension of serpentinite into the upper lithosphere was inferred to occur during Stage three; V5 type veins are associated with this stage. Textures and vein morphologies, representing supersaturated conditions and a decrease in temperature, were observed. Stage 4 (V6 type veins) was characterized by shear deformation features, which formed as a result of thrusting associated with the emplacement of the RGSB or Late Eocene transpression and fault reactivation along the Caribbean plate boundary.     

Organic fades in Recent sediments of carbonate platforms: Southwestern Puerto Rico and Northern Belize

Our organic facies model of a platform environment is based on the analysis of (1) total organic carbon, (2) visual protokerogen types and hydrogen indices of the sediments, (3) sediment mineralogy and grain size, and (4) reef patterns, water circulation, and relief of the adjacent land.TOC values are lowest on reefs and outer platforms (0.2%); intermediate in sediments fringing carbonate islands (0.5–2.0%), on sea-grass meadows (0.5–0.7%), and in forereef lagoons (0.1–0.7%); highest in inner platform lagoons (0.5–5.0%) and mangrove swamps (2.7–3.5%). Paniculate organic matter comprises structured terrestrial, marine, and amorphous types. On average, terrestrial material accounts for 28% of OM in Puerto Rico and 12% in Belize. The mean hydrogen index of the sediment is 355 (mg hydrocarbons/g TOC) in Puerto Rico and 719 in Belize.This study indicates that TOC values are mainly related to platform subenvironment, while OM types are controlled by distance from the shoreline. Organic facies dominated by structural terrestrial OM occur closer to the shore, whereas toward the shelf margin marine and amorphous OM contents increase.     

Composition and vertical flux of organic matter in a large Alaskan estuary

Observations of the composition and rate of input of organic matter to the sea floor were made at three locations in lower Cook Inlet, Alaska, during five cruises taken in the spring and summer of 1978. Total particulate, plant pigment, carbon, nitrogen, fecal pellet, and phytoplankton cell fluxes, inferred from sediment trap samples, were related to algal biomass and production in overlying waters. A daily average of 7.5% of the phytoplankton biomass was lost to the bottom. Of this loss, 83% was attributable to zooplankton grazing and fecal pellet production. At the three sampling sites, an average of 39 g C m^?2 (range of 17–60 g C m^?2, was sedimented to the bottom between May and August. This carbon flux represented an average of 12% of the total primary production measured for that time period. Kachemak Bay eastern arm of the inlet, is identified as an extremely productive embayment in which large amounts of organic matter were transferred to the sea floor.     

Sources,sinks and distribution of organic carbon in the St. Lawrence Estuary,Canada

Carbon isotope ratio analysis of particulate, planktonic, and sedimentary organic carbon and dissolved inorganic carbon has been used to study the sources and sinks of the organic carbon in the St. Lawrence Estuary and Gulf of St. Lawrence, Canada. Particulate organic carbon (POC) isotope ratios in the upper St. Lawrence Estuary are uniform and indistinguishable from those of POC in the St. Lawrence River and of planktonic organic carbon in both areas. The abundance of freshwater diatoms in the upper Estuary suggests that upper Estuary POC is predominantly “fresh” organic matter of riverborne origin. Upper Estuary POC is isotopically different from POC in the lower St. Lawrence Estuary and Gaspé regions, but is not different from POC from the surface waters of the open Gulf of St. Lawrence. The isotopic composition of planktonic organic carbon mirrors that of the POC, indicating that the POC in the lower Estuary and Gulf is also “fresh” organic matter. Since the lower Estuary POC forms an isotopic barrier between the upper Estuary POC and the Gulf of St. Lawrence POC, there appears to be little mixing of POC between these three reservoirs. Therefore POC in the lower Estuary and Gulf is most likely both produced and deposited (or degraded) in situ.An examination of carbon isotope ratio differences between the planktonic and dissolved inorganic carbon reservoirs shows that this difference varies significantly and somewhat unpredictably between sectors of the study area. Interpretation of environmental carbon isotope data on the basis of an assumed, constant fractionation factor may be subject to large errors. Direct measurement of both reservoirs is obviously preferable.     

Sources of Nutrients and Fecal Indicator Bacteria to Nearshore Waters on the North Shore of Kaua`i (Hawai`i,USA)

Water quality monitoring in Hanalei Bay, Kaua`i (Hawai`i, USA) has documented intermittent high concentrations of nutrients (nitrate, phosphate, silica, and ammonium) and fecal indicator bacteria (FIB, i.e., enterococci and Escherichia coli) in nearshore waters and spurred concern that contaminated groundwater might be discharging into the bay. The present study sought to identify and track sources of nutrients and FIB to four beaches in Hanalei Bay and one beach outside the bay, together representing a wide range of land uses. ²²³Ra and ²²⁴Ra activity, salinity, nutrient and FIB concentrations were measured in samples from the coastal aquifer, the nearshore ocean, springs, the Hanalei River, and smaller streams. In addition, FIB concentrations in beach sands were measured at each site, and the enterococcal surface protein (esp) gene assay was used to investigate whether the observed FIB originated from a human source. Nutrient concentrations in groundwater were significantly higher than in nearshore water, inversely correlated to salinity, and highly site specific, indicating local controls on groundwater quality. Fluxes of groundwater into Hanalei Bay were calculated using a mass-balance approach and represented at least 2–10% of river discharges. However, submarine groundwater discharge (SGD) may provide 2.7 times as much nitrate + nitrite to Hanalei Bay as does the Hanalei River. It may also provide significant fluxes of phosphate and ammonium, comprising 15% and 20% of Hanalei River inputs, respectively. SGD-derived silica inputs to the bay comprised less than 3% of Hanalei River inputs. FIB concentrations in groundwater were typically lower than those in nearshore water, suggesting that significant FIB inputs from SGD are unlikely. Positive esp gene assays suggested that some enterococci in environmental samples were of human fecal origin. Identifying how nutrients and FIB enter nearshore waters will help environmental managers address pressing water quality issues, including exceedances of the state Enterococcus water quality standard and nutrient loading to coral reefs.     

An organic geochemical investigation of the practice of manuring at a Minoan site on Pseira Island,Crete

Lipid components in a soil profile developed in an agricultural terrace at a Minoan site on Pseira Island, Crete, were analyzed to determine whether the practice of manuring in antiquity, as inferred by distributional and temporal sherd scatter, could be confirmed through the use of biomarker compounds as proxies for manuring. Analysis of total organic carbon and the abundance of n‐alkyl lipids (n‐alkanols and fatty acids) demonstrated that while the upper part of the soil profile had received more recent inputs of vegetation‐derived organic matter, the deeper archaeological strata remained essentially undisturbed. Further analysis of 5β‐stanols, sterol components which may be utilized as fecal biomarkers, revealed a signal indicative of manuring, with human or porcine‐derived fecal material, in the lower 15 cm of the profile. Additional appraisal of epicoprostanol abundance inferred the possible practice of composting in later periods. This study represents a detection of manuring, in the oldest samples to date, using organic geochemical methods. © 2001 John Wiley & Sons, Inc.     

First record of 1.2 Ga quartz dioritic magmatism in the Archaean Yilgarn Craton,Western Australia,and its significance

Farming of southern bluefin tuna in South Australia currently contributes to more than 30% of the value of the aquaculture production in Australia. This study investigated the natural sedimentary setting of the area designated for this important industry in coastal waters off Port Lincoln, and explored the links between the natural distribution of sediments and potential environmental effects and risks to the industry. Sediments were mostly composed of poorly sorted silts and fine sands, predominantly skeletal remains of carbonate-secreting organisms. The contribution of plankton to the organic matter remaining in the sediments was calculated to be in excess of 80% using concentration-dependent stable-isotope mixing models. An erosional area was identified south of Rabbit Island where sediments contained up to 50% siliciclastic material, grainsize distributions were better sorted and coarser, and organic carbon and total nitrogen contents were very low. In contrast, deeper waters north of Cape Donington were identified as a depocentre for fine sediments, which contained organic matter levels twice those elsewhere in the region despite the extremely high carbonate contents (>80%). The heavier stable isotopic signature of nitrogen suggested that this organic matter comprised a greater fraction of weathered components, probably advected to the area by suspended and bedload transport. This local variability of sediment characteristics in the farming zone suggests that the benthic assimilative capacity of farmed sites will depend on their location. Wastes from pens located south of Rabbit Island in particular are likely to be quickly winnowed out by wave and tidal action. These pens are also less likely to be affected by resuspension of fine sediments that might be associated with unusually severe storms.     

Unabated acid mine drainage from Cerro Rico de Potosí, Bolivia: uncommon constituents of concern impact the Rio Pilcomayo headwaters

Intensive mining and processing of the polymetallic sulfide ore body of Cerro Rico de Potosí (Bolivia) has occurred since 1545, leading to severe degradation of surface and subsurface waters, stream sediments, and soils at the headwaters of the economically vital, yet highly impacted, Rio Pilcomayo. Previous studies have documented extremely elevated concentrations of a limited suite of metals in local waterways from acid mine drainage (AMD), terrestrial and in-stream tailings, and ore processing plant discharges. However, contamination from a wider variety of ecotoxic metals/metalloids was considered likely due to the highly mineralized polymetallic nature of the ore body. To screen for this broader range of ecotoxic elements in AMD and receiving streams, data were gathered during two sampling events timed for the most extreme periods of the dry and wet seasons of one water-year. Concentrations of Ag, B, Ba, Mo, Sb, Se, Sn and V in AMD and receiving streams were greater than Bolivian discharge limits and receiving water body guidelines as well as international agricultural use standards. Locally, results indicate that contamination from mining Cerro Rico has a larger scope than previously thought and underscore the importance of remediation. Globally, the results raise the possibility that other mining regions could have unquantified hazards from overlooked ecotoxic elements and that screening for a broader range of contaminants may be warranted.     

Controls on salt marsh accretion: A test in salt marshes of Eastern Canada

We used¹³⁷Cs-dating to determine vertical accretion rates of 15 salt marshes on the Bay of Fundy, the Gulf of St. Lawrence, and the Atlantic coast of Nova Scotia. Accretion rates are compared to a number of factors assumed to influence vertical marsh accretion: rates of relative sea-level rise, climatic parameters (average daily temperatures and degree days) and latitude (related to insolation and day length), sediment characteristics (organic matter inventory, bulk, mineral, and organic matter density), distance of the core site from the nearest source of tidal waters, and the tidal range. Uniques to our study is a consideration of climatic parameters and latitude, which should influence organic matter production, and thus vertical accretion rates. Significant predictors of accretion rates (in order of importance) were found to be organic matter inventory, distance from a creek, and range of mean tides. Contrary to conclusions from previous studies, we found that accretion rates decreased with increasing tidal range, probably because we considered a wider span of tidal ranges, from micro- to macrotidal. Although four marshes with low organic matter inventories also show a deficit in accretion with respect to relative sea-level rise, organic matter is not limiting in two-thirds of the marshes studied, despite shorter growing seasons.     

Geoarchaeological Investigations of Midden‐Formation Processes in the Early to Late Ceramic Neolithic Levels at Çatalhöyük,Turkey ca. 8550–8370 cal BP

Anthropogenic midden deposits are remarkably well preserved at the Neolithic settlement of Çatalhöyük and provide significant archaeological information on the types and nature of activities occurring at the site. To decipher their complex stratigraphy and to investigate formation processes, a combination of geoarchaeological techniques was used. Deposits were investigated from the early ceramic to late Neolithic levels, targeting continuous sequences to examine high resolution and broader scale changes in deposition. Thin‐section micromorphology combined with targeted phytolith and geochemical analyses indicates they are composed of a diverse range of ashes and other charred and siliceous plant materials, with inputs of decayed plants and organic matter, fecal waste, and sedimentary aggregates, each with diverse depositional pathways. Activities identified include in situ burning, with a range of different fuel types that may be associated with different activities. The complexity and heterogeneity of the midden deposits, and thus the necessity of employing an integrated microstratigraphic approach is demonstrated, as a prerequisite for cultural and palaeoenvironmental reconstructions.     

Acid mine drainage at Cerro Rico de Potosí II: severe degradation of the Upper Rio Pilcomayo watershed

Ag, Pb, Sn and Zn ores have been intensively mined and processed at Cerro Rico de Potosí, Bolivia since 1545. Acid mine drainage (AMD) and mineral processing plant effluent are prime sources of water contamination in the headwaters of the Upper Rio Pilcomayo watershed. Streams receiving AMD drainage from the slopes of Cerro Rico and surrounding landscapes were sampled during the dry (July–August 2006) and wet (March 2007) seasons of one water-year. In-stream waters contained total metal concentrations of up to 16 mg/L As, 4.9 mg/L Cd, 0.97 mg/L Co, 1,100 mg/L Fe, 110 mg/L Mn, 4.1 mg/L Pb, and 1,500 mg/L Zn with pH ranging from 2.8 to 9.5. AMD-impacted streams contained elevated concentrations of the same major ecotoxic constituents present in AMD discharges at concentrations orders of magnitude greater than in those streams unimpacted by AMD. Many of the AMD impacted water bodies are more degraded than class “D” of the Bolivian receiving water body criteria, rendering them unfit for domestic or agricultural use. Natural attenuation is insufficient to render waters safe for use, however, some of these waters are currently being utilized for irrigation and livestock watering. The data indicate that historic and current mining activities have transformed these key natural resources into potential human and environmental health hazards.     

Evaluation of bank filtration as a pretreatment method for the provision of hygienically safe drinking water in Norway: results from monitoring at two full-scale sites

Two case studies were carried out in central Norway in order to assess the performance of bank filtration systems in cold-climate fluvial aquifers relying on recharge from humic-rich surface waters with moderate microbial contamination. Three municipal wells and two surface-water sources at operative bank filtration systems were monitored for naturally occurring bacteriophages, fecal indicators, natural organic matter (NOM) and physico-chemical water quality parameters during a 4-month period. Aquifer passage effectively reduced the microorganism and NOM concentrations at both study sites. Bacteriophages were detected in 13 of 16 (81%) surface-water samples and in 4 of 24 (17%) well-water samples, and underwent 3 ± 0.3 log₁₀ reduction after 50–80-m filtration and 20–30 days of subsurface passage. NOM reductions (color: 74–97%; dissolved organic carbon: 54–80%; very hydrophobic acids: 70%) were similar to those achieved by conventional water-treatment processes and no further treatment was needed. Both groundwater dilution and sediment filtration contributed to the hygienic water quality improvements, but sediment filtration appeared to be the most important process with regard to microbial and NOM reductions. A strengths-weaknesses-opportunities-threats analysis showed that bank filtration technology has a high potential as a pretreatment method for the provision of hygienically safe drinking water in Norway.     

A geochemical evaluation of perennial spring activity and associated mineral precipitates at Expedition Fjord,Axel Heiberg Island,Canadian High Arctic

Two groups of perennial springs are observed in the Canadian High Arctic at Expedition Fjord on Axel Heiberg Island at Colour Peak and Gypsum Hill. Saline discharge (∼1.3–2.5 molal NaCl) produces a variety of calcite (travertine) and gypsum-rich precipitates. Saturation index calculations of the spring waters at Colour Peak suggest CO₂ degassing from the waters causes calcite precipitation. Gypsum precipitation dominates at Gypsum Hill, where spring waters have lower alkalinity and higher SO₄ concentrations. Mineral accumulations form both channel and rimstone pool morphologies as a result of varying slope conditions. At Colour Peak, confined flow in steep slope areas develop massive structures in contrast to more friable, porous accumulations in areas where waters fan out on shallower slopes; these morphological variations lead to corresponding varying apparent rates of mineral precipitation. Mineral precipitation at Gypsum Hill is far less notable as a result of lower discharge rates and annual degradation by icing formation. Microscopic observations and geochemical analyses of the channel precipitates at Colour Peak reveal alternating light (calcite spar) and dark (anhedral microcrystalline calcite combined with organic matter and non-carbonate minerals) laminae. Rimstone pools forming in lower sections of spring discharge are composed of accumulations of large euhedral calcite crystals interbedded with allochthonous inputs. High concentration of dissolved solids is responsible for slow travertine precipitation rates, which occurs during winter. This precipitation is further retarded during summer months by the introduction of crystal growth inhibitors such as Fe³⁺ and deposition of organic matter and soil sediments.     

Survival of F-RNA coliphages and three bacterial indicators during wastewater chlorination and transport in estuarine waters

Three bacterial water quality indicators,Clostridium perfringens, enterococci, and fecal coliforms, were compared to F-RNA coliphages for their survival during chlorination at several municipal wastewater treatment plants in Rhode Island and seasonally during transport in a section of the Narragansett Bay estuary. F-RNA coliphages were used as the best available indicator for the survival of Noroviruses (formerly Norwalk-like virus), the most frequently identified agent for the most prevalent waterborne disease (an acute but benign gastroenteritis), which has yet to be propagated in tissue culture and for which there is no lower animal model. Inactivation of the enterococci and fecal coliforms during wastewater chlorination was much greater than that of the F-RNA coliphages whose inactivation was essentially the same as that of C.perfringens. Survival of the F-RNA coliphages andC. perfringens during winter transport down Narragansett Bay were comparable to each other and greater than that for the enterococci or fecal coliforms. During the summer,C. perfringens survived longer than the other three indicators, possibly because the virus-like (F-RNA coliphages) and the two vegetative bacterial indicators were more susceptible than theC. perfringens spores to the lethal effects of sunlight and elevated water temperatures during the summer. Based on these findings, F-RNA coliphages seems to be a reliable indicator of viral contamination and die-off in estuarine waters.     

Chemical behavior of the Salí River, Province of Tucumán, Argentina

Major ionic composition and other chemical parameters were determined at five sampling stations on the Salí River (Province of Tucumán, Argentina). The heavy human usage of the river causes increased levels of dissolved ions, from the dissolution of halite and gypsum, and from the weathering of basic sediments. Correlations demonstrate that sodium chloride and sulphate, and calcium carbonate are the main contributors to dissolved ions in the river. In the polluted region, south of the Celestino Gelsi dam, the main source of calcium and sulphate is the dissolution of gypsum. Large amounts of halite are also dissolved. Weathering of biotite, K-feldspar and albite are suggested by the data. Conductivity, dissolved oxygen and organic matter all indicate severe contamination by organic matter (mainly from sugar-cane processing) in the lower course. The data also demonstrate a substantial improvement in water quality before the discharge of the river at the Río Hondo dam. Data from the Colorado (a tributary of the Salí River) and Medina rivers are also analyzed and compared.     

Application of pyrolysis–GC/MS for the characterisation of suspended particulate organic matter in the Mediterranean Sea: a comparison with the Black Sea

Suspended particulate organic matter (SPOM) both from the oligotrophic Mediterranean and from the more productive Black Sea has been analysed by pyrolysis–gas chromatography/mass spectrometry (Py–GC/MS) and by such conventional techniques as elemental analysis and fluorometry. The data achieved by the two approaches generally confirmed and complemented each other. The relative concentrations of pyrolysis products (termed markers) characteristic of chlorophyll (CHL), lipid, carbohydrate (CBH), and protein (PROT) components of SPOM have been determined. The vertical distribution of lipid markers was more uniform in the Mediterranean surface waters. Their relative abundance increased rapidly in the oxycline of the Black Sea, reaching their highest levels in the suboxic zone, where the protein composition of the SPOM changed significantly. In both seas, the relative concentrations of CHL markers increased consistently within the CHL maximum zone where the CBH markers were less abundant. No lignin markers from terrestrial vegetation were detected at significant levels in the pyrograms.     

A Comparison of Water Quality Between Low- and High-Flow River Conditions in a Tropical Estuary, Hilo Bay, Hawaii

Effects of storms on the water quality of Hilo Bay, Hawaii, were examined by sampling surface waters at 6 stations 10 times during low-flow and 18 times during high-flow (storms) river conditions. The direction of a storm’s impact on water quality parameters was consistent among storms and most stations; however, direction of the impact varied with the parameter. High river flow conditions increased concentrations of nitrate and decreased those of dissolved organic nitrogen (N); effects on ammonium and particulate N were station specific. Storms also increased dissolved organic and particulate carbon (C) concentrations. Dissolved phosphorus (P) concentrations were not affected by high river flow events. Dissolved organic forms dominated the N, C, and P pools under both low- and high-flow river conditions. Soil-derived particles and fecal indicator bacteria increased during storms, while chlorophyll a concentrations and bacterial cell abundances decreased. Our results suggest that an increase in storms with global warming could impact water quality of tropical estuaries.     

Chronology,stratigraphy and palaeoenvironmental interpretation of a Late Pleistocene to mid‐Holocene cave accumulation on Kangaroo Island,South Australia

Chronological, sedimentological and geochemical analyses of a clastic infill from Kelly Hill Cave (5K1), Kangaroo Island, document a palaeoenvironmental record that spans from the Late Pleistocene to the middle Holocene. We AMS radiocarbon‐dated bone collagen and U–Th‐dated speleothem to determine that fossiliferous sediments were deposited between >20 ka and 7 ka ago. Most of the 15 sedimentary layers are dominated by sand‐ and silt‐sized quartz that is physically and geochemically comparable with surface soils in the Kelly Hill area. Late Pleistocene and Last Glacial Maximum strata are represented primarily by homogeneous, poorly sorted quartz‐rich sediments that contain little organic matter, but include a thin layer composed largely of silt‐sized clay pellets that resemble sediments deflated from playa lakes. Microstructures observed in petrographic slides indicate that, with the exception of one layer, all sediments experienced little reworking once deposited in the cave. Some layers display pedogenic microstructures such as redeposited clays and opaline silica infilling that indicate postdepositional modification; that is, cave‐floor soil development. Overlying Holocene‐aged sediments also consist mainly of quartz but have much greater organic matter content. Some of these sediments have been strongly influenced by re‐precipitated organic matter that appears to have been transported into the cave via vadose drip water. The presence of dissolved organic matter in soil/vadose waters suggests a high vegetation density and acidic soils, which are congruent with the more equitable climatic conditions characteristic of the Holocene. The sediments described here provide a valuable palaeoenvironmental record that will facilitate future interpretation of associated vertebrate fossils.     

Sedimentary organic matter record of recent environmental changes in the St. Marys River ecosystem,Michigan–Ontario border

Lake George, located in the St. Marys River, has been heavily impacted by human-induced environmental changes over the past century. The effects of human impacts starting in the late nineteenth century and of natural, gradual diagenesis can be distinguished in the bulk organic matter and molecular contents of the sedimentary record. Organic carbon concentrations increase from 0.5% in sediments deposited 200 years ago to ∼4% in recent sediments. A fourfold increase in organic carbon mass accumulation rates accompanies the change in concentrations. Elevated C/N ratios in near-modern sediments indicate that increased delivery of land-derived organic matter has been responsible for much of the recent increases in sedimentary organic carbon. Organic δ¹³C and δ¹⁵N values change significantly and coincidentally with the environmental changes, reflecting depressed algal productivity since the introduction of industrial effluents to the aquatic system, increased delivery of land-derived organic matter and some impacts of acid rain. Increases in microbial and petroleum hydrocarbon contributions occur in sediments deposited since 1900. Fatty acid distributions provide evidence of substantial microbial reworking of organic matter throughout the sedimentary record.     

Cycling of trace metals (Mn, Fe, Mo, U, V, Cr) in deep pore waters of intertidal flat sediments

Trace metals (Mn, Fe, Mo, U, Cr, V) were studied in pore waters of an intertidal flat located in the German Wadden Sea. The study system is an example of a permeable tidal flat system where pore water exchange is affected by tidal driven pressure gradients besides diffusion. Permanently installed in situ samplers were used to extract pore waters down to 5 m depth throughout one year. The samplers were either located close to the tidal flat margin or in central parts of the tidal flat. Despite dynamic sedimentological and hydrological conditions, the general trends with depth in deep tidal flat pore waters are remarkably similar to those observed in deep sea environments. Rates of trace metal cycling must be comparably large in order to maintain the observed pore water profiles. Trace metals further show similar general trends with depth close to the margin and in central parts of the tidal flat. Seasonal sampling revealed that V and Cr vary concurrent with seasonal changes in dissolved organic carbon (DOC) concentration. This effect is most notable close to the tidal flat margin where sulphate, DOC, and nutrients vary with season down to some metres depth. Seasonal variations of Mn, Fe, Mo, and U are by contrast limited to the upper decimetres of the sediment. Their seasonal patterns depend on organic matter supply, redox stratification, and particulate matter deposited on sediment surfaces. Pore water sampling within one tidal cycle provides evidence for pore water advection in margin sediments. During low tide pore water flow towards the creekbank is generated by a hydraulic gradient suggesting that deep pore waters may be seeping out of creekbank sediments. Owing to the enrichment of specific elements like Mn in pore water compared to sea water, seeping pore waters may have an impact on the chemistry of the open water column. Mass balance calculations reveal that the impact of deep pore waters on the Mn budget in the open water column is below 4%. Mn deep pore water discharge of the whole Wadden Sea is estimated to be about 9% of the total dissolved riverine Mn input into the Southern North Sea.