Trace Metal Fluxes Research Articles

Early atmospheric contamination on the top of the Himalayas since the onset of the European Industrial Revolution

Because few ice core records from the Himalayas exist, understanding of the onset and timing of the human impact on the atmosphere of the "roof of the world" remains poorly constrained. We report a continuous 500-y trace metal ice core record from the Dasuopu glacier (7,200 m, central Himalayas), the highest drilling site on Earth. We show that an early contamination from toxic trace metals, particularly Cd, Cr, Mo, Ni, Sb, and Zn, emerged at high elevation in the Himalayas at the onset of the European Industrial Revolution (∼1780 AD). This was amplified by the intensification of the snow accumulation (+50% at Dasuopu) likely linked to the meridional displacement of the winter westerlies from 1810 until 1880 AD. During this period, the flux and crustal enrichment factors of the toxic trace metals were augmented by factors of 2 to 4 and 2 to 6, respectively. We suggest this contamination was the consequence of the long-range transport and wet deposition of fly ash from the combustion of coal (likely from Western Europe where it was almost entirely produced and used during the 19th century) with a possible contribution from the synchronous increase in biomass burning emissions from deforestation in the Northern Hemisphere. The snow accumulation decreased and dry winters were reestablished in Dasuopu after 1880 AD when lower than expected toxic metal levels were recorded. This indicates that contamination on the top of the Himalayas depended primarily on multidecadal changes in atmospheric circulation and secondarily on variations in emission sources during the last 200 y.

Benthic trace metal fluxes in a heavily contaminated bay in China: Does the sediment become a source of metals to the water column?

Over three different seasons, seawater, porewater and sediment samples were collected from Jinzhou Bay, a previously heavily contaminated bay, to quantitatively assess the benthic flux of trace metals after a reduction in fluvial/sewage discharge for almost three decades. The spatial distribution patterns of trace metals in seawater, surface sediment, as well as the vertical distribution patterns of metals in porewater and solid phases in short sediment cores were reported. Metal concentrations in seawater and sediment all showed much higher Cd and Zn concentrations inside the Jinzhou Bay compared to the rest of Bohai Sea area. Zn, Ni, Pb and Co all had average benthic fluxes coming out of the sediments to the water column, contributing about 0.5%, 0.3%, 1.4% and 14% to their current standing stock in Jinzhou Bay. Seasonal difference was also identified in seawater and porewater, as well as in the benthic fluxes. In general, benthic fluxes and porewater concentrations all tended to be higher in summer, implying a close relationship between benthic flux and the temperature-dependent organic matter degradation process at the sediment-water interface.Currently, there are clearly still other sources, possibly fluvial/sewage discharge, as the main source of trace metals in Jinzhou Bay waters. For Cd and Cu, concentrations in the water column remain high on an annual basis indicating that sediment still acts as a sink. Conversely, for Pb, Zn, Co, and Ni, the sediment is beginning to act as a source to the water column. Although this may not yet be significant, it will become more and more important with time, and can last for hundreds to thousands of years.

Nutrient and Trace Metal Fluxes into Estuarine Sediments Linked to Historical and Expanding Agricultural Activity (Hearnes Lake, Australia)

Agriculture activities in coastal catchments often contribute pollutant runoff such as nitrogen (N), phosphorus (P), and trace metals to estuarine environments. Here, we determine the historical impacts from agricultural expansion using sediment samples from an estuary and a coastal wetland downstream from intensive historical banana, and now, blueberry plantations (Hearnes Lake estuary, NSW, Australia). The three 210Pb dated sediment cores and surface sediment samples analyzed in this study revealed that trace metals (As, Cd, Cu, Pb, Zn, Cr) and N fluxes recently increased as a result of increasing sedimentation rates. Several moderate localized enrichments were observed in recent sediment layers. Most importantly, we found a clear link between the sediment P profile and recent blueberry cultivation. P enrichment increased by 9-fold and sediment fluxes by over 40-fold (up to 12.6 mg m−2 year−1) during the expansion of blueberry cultivation within the catchment since 2002. The trapping of sediments enriched in P by the wetlands provided a good chronology of agricultural practices in the region. With a global and regional increase in estuarine eutrophication, this study further demonstrates the importance of agricultural sources and the role coastal wetlands play in sequestering P from runoff.

Tidal induced dynamics and geochemical reactions of trace metals (Fe, Mn, and Sr) in the salinity transition zone of an intertidal aquifer

Biogeochemical reactions in an intertidal aquifer influences the submarine groundwater discharge (SGD) associated trace metal flux to the ocean. Tidal fluctuation greatly affects the physical mixing, and biogeochemical transformation of trace metals in the intertidal aquifer. This study presents the dynamics of trace metals (Fe, Mn, and Sr) and the production of Fe2+ in the salinity transition zone is discovered. The variations of Fe2+ are led by the shifts of both physical mixing and biogeochemical reaction during tidal fluctuation. The transformation from amorphous Fe(OH)3 to FeS is the main reason for the enrichment of Fe2+ in the zone with a salinity of 0.5–10. Mn behaves much less active than Fe in the intertidal aquifer due to the very limited Mn in the solid phase and the major driving force of Mn2+ variation is the physical mixing rather than geochemical reaction. Sr2+ behaves conservatively and shows a synchronous with salinity in the salinity transition zone. This study found that Fe2+ precipitates in a form not limited to Fe (hydro)oxides and the FeS minerals is the most possible form of precipitation in reduced aquifers. In that case, only a small part of Fe2+ discharges to the sea associated with SGD, but Mn2+ has a comparatively conservative property during the transport in the intertidal aquifer and majority of the Mn2+ originated from fresh groundwater will discharge with SGD in this study. The biogeochemical transformation pathways of Fe and Mn observed in this study provides insights into the cycles of Fe and Mn in an intertidal aquifer, which is of significance to accurately estimate the SGD derived Fe and Mn fluxes to the ocean.

Bulk/wet deposition of trace metals to rural, industrial, and urban areas in the Yangtze River Delta, China

The bulk depositions of trace metals to three land uses in the Yangtze River Delta are investigated based on the collected 154 precipitation samples from August 2015 to May 2017. The volume-weighted mean (VWM) concentrations of Ni, Cu, Zn, Cd, and Pb were 13.28, 5.32, 13.02, 0.33, and 10.53 μg L−1, and 12%, 16%, 3%, 11%, and 26% of precipitation events exceeded the limits in the Central Drinking-Water Source Area (GB3838-2002), respectively. Furthermore, the five metals varied significantly under urban, industrial, and rural land use conditions, indicating that these metal concentrations were greatly determined by local sources; lower concentrations were found in sea and local air masses than in air masses from inland trajectories. Combining the precipitation amounts, the bulk deposition fluxes of the five metals were 25.99, 25.47, 20.60, 10.40, 0.64 mg m−2 yr−1. By comparing the metal deposition fluxes in 98 studies across China, Ni and Pb deposition in the Yangtze River Delta was higher, while that of Cd and Zn was lower than their respective averages across China, indicating that Ni and Pb pollution should receive more attention in the study area. CapsuleBulk/wet deposition fluxes of trace metals varied greatly among rural, industrial, and urban areas, and Pb and Ni showed severe pollution levels in the Yangtze River Delta.

Benthic fluxes of trace metals in the Chukchi Sea and their transport into the Arctic Ocean

The Chukchi Sea is a primary site for shelf-ocean exchange in the Arctic region and modifies Pacific-sourced water masses as they transit via the Bering Strait into the Arctic Ocean. The aim of this study was to use radium and trace metal distributions to improve our understanding of biogeochemical cycles in the Bering and Chukchi Seas, and evaluate their potential response to future changes in the Arctic. We investigated the distributions of dissolved and total dissolvable trace metals (Cd, Fe, Ni, Cu, Zn, Mn, Co, and Pb) in the Bering and Chukchi Seas during spring. In addition, the long-lived radium isotopes (226Ra and 228Ra) were measured as tracers of benthic trace metal inputs. Trace metal concentrations, especially Fe and Mn, were highly elevated in Chukchi shelf waters compared with the open Arctic Ocean and Bering Strait. Trace metal, nutrient, and Ra patterns suggested that Fe, Mn, and Co concentrations were predominantly controlled by reductive benthic inputs, whereas the other trace metals were influenced by biological uptake and release processes. We propose that Fe, Mn, and Co in the Chukchi Sea are supplied from shelf sediments during winter overturning, and we combine the 228Ra fluxes with the distributions of Fe, Mn, and Co to provide a first estimate of their benthic fluxes in the region. The average benthic flux of 228Ra was 1.49 × 108 atoms m−2 d−1, which is among the highest rates reported globally. Estimated dissolved Fe (D-Fe) flux from the sediments was 2.5 μmol m−2 d−1, whereas D-Mn and D-Co fluxes were 8.0 μmol m−2 d−1 and 0.2 μmol m−2 d−1, respectively. The off-shelf transport of D-Fe to the Arctic Ocean is estimated to be about 10–25% of the benthic Fe flux, with the remainder retained on the shelf due to scavenging and/or phytoplankton uptake. Our results highlight the importance of the Chukchi Sea as a major source of the micro-nutrients to the Arctic Ocean, thereby supporting primary production. Long-term changes in factors that affect cross-shelf mixing, such as the observed reduction in ice cover, may therefore enhance shelf nutrient inputs and primary productivity in the Arctic.

Tracing silicate weathering processes in the permafrost-dominated Lena River watershed using lithium isotopes

Increasing global temperatures are causing widespread changes in the Arctic, including permafrost thawing and altered freshwater inputs and trace metal and carbon fluxes into the ocean and atmosphere. Changes in the permafrost active layer thickness can affect subsurface water flow-paths and water-rock interaction times, and hence weathering processes. Riverine lithium isotope ratios (reported as δ7Li) are tracers of silicate weathering that are unaffected by biological uptake, redox, carbonate weathering and primary lithology. Here we use Li isotopes to examine silicate weathering processes in one of the largest Russian Arctic rivers: the Lena River in eastern Siberia. The Lena River watershed is a large multi-lithological catchment, underlain by continuous permafrost. An extensive dataset of dissolved Li isotopic compositions of waters from the Lena River main channel, two main tributaries (the Aldan and Viliui Rivers) and a range of smaller sub-tributaries are presented from the post-spring flood/early-summer period at the onset of active layer development and enhanced water-rock interactions. The Lena River main channel (average δ7Lidiss ∼ 19‰) has a slightly lower isotopic composition than the mean global average of 23‰ (Huh et al., 1998a). The greatest range of [Li] and δ7Lidiss are observed in catchments draining the south-facing slopes of the Verkhoyansk Mountain Range. South-facing slopes in high-latitude, permafrost-dominated regions are typically characterised by increased summer insolation and higher daytime temperatures relative to other slope aspects. The increased solar radiation on south-facing catchments promotes repeated freeze-thaw cycles, and contributes to more rapid melting of snow cover, warmer soils, and increased active layer thaw depths. The greater variability in δ7Li and [Li] in the south-facing rivers likely reflect the greater infiltration of melt water and enhanced water-rock interactions within the active layer.A similar magnitude of isotopic fractionation is observed between the low-lying regions of the Central Siberian Plateau (and catchments draining into the Viliui River), and catchments draining the Verkhoyansk Mountain Range into the Aldan River. This is in contrast to global rivers in non-permafrost terrains that drain high elevations or areas of rapid uplift, where high degrees of physical erosion promote dissolution of freshly exposed primary rock typically yielding low δ7Lidiss, and low-lying regions exhibit high riverine δ7Li values resulting from greater water-rock interaction and formation of secondary mineral that fractionates Li isotopes. Overall, the range of Li concentrations and δ7Lidiss observed within the Lena River catchment are comparable to global rivers located in temperate and tropical regions. This suggests that cryogenic weathering features specific to permafrost regions (such as the continual exposure of fresh primary minerals due to seasonal freeze-thaw cycles, frost shattering and salt weathering), and climate (temperature and runoff), are not a dominant control on δ7Li variations. Despite vastly different climatic and weathering regimes, the same range of riverine δ7Li values globally suggests that the same processes govern Li geochemistry – that is, the balance between primary silicate mineral dissolution and the formation (or exchange with) secondary minerals. This has implications for the use of δ7Li as a palaeo-weathering tracer for interpreting changes in past weathering regimes.

Physical and chemical parameters and trace metal flux in water, soil and plant samples collected from industrial effluent affected areas in and around Dhaka city

Water and soil samples were collected from five different industrial areas around Dhaka city namely, (i) Powertex Fashion Ltd., Gazipur (Textile), (ii) Shetu Pesticide Ltd., Savar (Pesticide), (iii) Salma Leather Industry, Hazaribagh (Tannery), (iv) Monno Ceramic Industries, Nayarhat, Dhamrai, (Ceramic) and (v) ACME Laboratories Ltd., Tulivita, Dhamrai (Pharmaceutical) where selected for this study. Two plants species viz. Colocasia esculenta (L.) Schott and Ipomoea aquatica Forssk. commonly growing in the industrial effluent affected areas were selected to observe the rate of heavy metal uptake. Dissolved oxygen (DO) was found below the permissible limit in all the affected areas (lowest 0.88 mg/l in tannery waste affected areas) indicating high amount of organic wastage discharge from tannery. Eight trace metals viz. arsenic, cadmium, nickel, iron, zinc, chromium, copper and lead were analysed for water, soil and plant samples. Arsenic and cadmium exceeded the permissible limit in water sample collected from all affected areas. Tannery waste affected area was found to be the most vulnerable area in respect to arsenic and chromium contamination. On the other hand, the highest amount of arsenic was found in the soil sample collected from pesticide affected area. The rate of heavy metal uptake in Colocasia esculenta (L.) Schott is much higher than Ipomoea aquatica Forssk. More heavy metals were accumulated in edible portion than roots of the plants.

Trace metal characterization and fluxes from the Guadiana, Tinto-Odiel and Guadalquivir estuaries to the Gulf of Cadiz

Metals transported into the coastal zone by the South Iberian rivers are key to understand the biogeochemical cycles and distribution of trace elements in the Gulf of Cadiz (GoC hereinafter) and the exchange with the Mediterranean Sea. Previous studies carried out in the 80s have suggested that metal enrichment in the Alboran Sea (Western Mediterranean) is related with fluvial inputs from acid mine drainage from the Tinto and Odiel rivers. The present study evaluates the contribution of dissolved trace metal concentrations (i.e. Cd, Co, Cu, Fe, Mo, Ni, Pb, V, Zn) from the three main rivers discharging into the GoC (i.e. Guadiana, Tinto-Odiel and Guadalquivir rivers). Our results show that the metal composition of water discharged from each river is impacted by the activities developed in the course of the rivers, which clearly influence the GoC coastal surface waters composition. Metal fluxes from the Guadalquivir river are quantitatively higher than those from the Tinto-Odiel (e.g. up to 73% and 19% higher for Ni and Cu, respectively). Although the metal concentrations spatial distributions in the GoC are dominated by the circulation pattern between the Atlantic and the Mediterranean Sea, the concentrations within the GoC continental shelf could be explained by a greater contribution from the Guadalquivir estuary (e.g. 80.5%, 54.6%, 56.5% and 56.6% for Ni, Cu, Mo, and V respectively).

Sediment evidence of industrial leakage-induced asynchronous changes in polycyclic aromatic hydrocarbons and trace metals from a sub-trophic lake, southwest China.

It has been well established that regional patterns of atmosphere-borne polycyclic aromatic hydrocarbons (PAHs) and trace metals were predominantly associated with the trajectory of socio-economic development; however, they could be potentially modulated by anthropogenic fingerprint of local sources such as industrial spill. Here, we established historical pollution data of both PAHs and trace metals from a well-dated sediment core from Yangzong Lake of Southwest China, which experienced a severe tailing leakage accident derived from a zinc concentrate smelting plant in 2007, aiming to evaluate the heterogeneity in their temporal trajectories and their sources of contamination in the context of regional deposition patterns. Sedimentary records show that the concentrations and fluxes of both PAHs and trace metals remained a consistently low level before the 1950s. An increasing trend and the synchronous changes of both PAHs and trace metals during ~ 1950-2002 were well consistent with the temporal pattern of socio-economic development in western China, with coal combustion and smelting industries as the main sources of contamination in this region. However, arsenic (As) and PAHs exhibited a concurrent spike for the period of ~ 2007-2013, contrasting strongly to the regional pattern of these contaminants. The modern concentrations of As revealed a 5- to 14-fold increase over the pre-1950 level, with the contemporary concentrations of PAHs rising by ~ 10-14 times. The sediment records reveal that local fingerprints of smelting activities in the catchment of Yangzong Lake have overridden the temporary pattern of regional atmosphere-borne As and PAHs over the last decade. This highlights the important role of local pollution sources in modulating or even overriding the regional pattern of anthropogenic contamination in highly impacted systems.

Lead isotopes as particulate contaminant tracers and chronostratigraphic markers in lake sediments in northeastern North America

The utility of lead (Pb) isotopes as tracers of particulate contamination and as chronostratigraphic markers was assessed in five lake sediment cores from the Great Lakes and southern Ontario region. The marker for smelting of highly radiogenic ores in the Upper Mississippi Valley in the mid-19th century was seen in the Pb isotopes in four lakes expanding the geographic range of this established marker into southern and central Ontario. This marker is useful for age-dating sediments deposited in the 1800s in archives where it is present. The estimated dates for this ~1850 marker using other dating methods span a range of 57years, emphasizing the importance of the marker as a tie-point for extrapolated dates in the 19th century. Lead isotopes identified leaded gasoline as an important source only in one lake in the second half of the 20th century; its signal was not identified in all other lakes because the lakes were more affected by local and regional inputs. Lead isotopes combined with trace metal fluxes identified a potential marker for coal combustion or urban sources in the second half of the 20th century in southern Ontario, where these sources were significant enough to outweigh leaded gasoline input. The effects of Canadian mining and smelting activities were seen in the trace metal flux profiles of central Ontario lakes; however, these activities were not visible in the Pb isotopes, likely due to mixing of several sources with similar Pb isotopic signatures. This study demonstrates the usefulness of combining lead isotopes and trace metal flux profiles for identifying markers of historical and modern particulate contamination sources, especially in regions where several pollution sources exist.

Estimating chemical composition of atmospheric deposition fluxes from mineral insoluble particles deposition collected in the western Mediterranean region

Abstract. In order to measure the mass flux of atmospheric insoluble deposition and to constrain regional models of dust simulation, a network of automatic deposition collectors (CARAGA) has been installed throughout the western Mediterranean Basin. Weekly samples of the insoluble fraction of total atmospheric deposition were collected concurrently on filters at five sites including four on western Mediterranean islands (Frioul and Corsica, France; Mallorca, Spain; and Lampedusa, Italy) and one in the southern French Alps (Le Casset), and a weighing and ignition protocol was applied in order to quantify their mineral fraction. Atmospheric deposition is both a strong source of nutrients and metals for marine ecosystems in this area. However, there are few data on trace-metal deposition in the literature, since their deposition measurement is difficult to perform. In order to obtain more information from CARAGA atmospheric deposition samples, this study aimed to test their relevance in estimating elemental fluxes in addition to total mass fluxes. The elemental chemical analysis of ashed CARAGA filter samples was based on an acid digestion and an elemental analysis by inductively coupled plasma atomic emission spectroscopy (ICP-AES) and mass spectrometry (MS) in a clean room. The sampling and analytical protocols were tested to determine the elemental composition for mineral dust tracers (Al, Ca, K, Mg and Ti), nutrients (P and Fe) and trace metals (Cd, Co, Cr, Cu, Mn, Ni, V and Zn) from simulated wet deposition of dust analogues and traffic soot. The relative mass loss by dissolution in wet deposition was lower than 1 % for Al and Fe, and reached 13 % for P due to its larger solubility in water. For trace metals, this loss represented less than 3 % of the total mass concentration, except for Zn, Cu and Mn for which it could reach 10 %, especially in traffic soot. The chemical contamination during analysis was negligible for all the elements except for Cd, which has a very low concentration in dust. Tests allowed us to conclude that the CARAGA samples could be used to estimate the contents of nutrients and trace metals in the limits of loss by dissolution. Chemical characterization of CARAGA deposition samples corresponding to the most intense dust deposition events recorded between 2011 and 2013 has been performed and showed elemental mass ratios consistent with the ones found in the literature for Saharan dust. However, the chemical analysis of CARAGA samples revealed the presence of some anthropogenic signatures, for instance high Zn concentrations in some samples in Lampedusa, and also pointed out that mineral dust can be mixed with anthropogenic compounds in the deposition samples collected on Frioul. Results showed that the chemical analysis of CARAGA ashed samples can be used to trace the origins of elemental deposition. The elemental atmospheric fluxes estimated from these chemical analyses of samples from the CARAGA network of weekly deposition monitoring constitute the first assessment of mass deposition fluxes of trace metals and P during intense dust deposition events at the scale of the western Mediterranean Basin. The mass fluxes strongly depend on the distance from dust sources and the most intense events, while proximity from anthropogenic sources strongly impacted the masse fluxes of Zn and Cu at Lampedusa and Frioul.

The competition between coastal trace metal fluxes and oceanic mixing from the 10Be/9Be ratio: Implications for sedimentary records

AbstractAt an ocean margin site 37°S offshore Chile, we use the meteoric cosmogenic 10Be/9Be ratio to trace changes in terrestrial particulate composition due to exchange with seawater. We analyzed the marine authigenic phase in surface sediments along a coast‐perpendicular transect and compared to samples from their riverine source. We find evidence for growth of authigenic rims through coprecipitation, not via reversible adsorption, that incorporate an open ocean 10Be/9Be signature from a deep water source only 30 km from the coast, overprinting terrestrial 10Be/9Be signatures. Together with increasing 10Be/9Be ratios, particulate‐bound Fe concentrations increase, which we attribute to release of Fe‐rich pore waters during boundary exchange in the sediment. The implications for the use of 10Be/9Be in sedimentary records for paleodenudation flux reconstructions are the following: in coast‐proximal sites the authigenic record will likely preserve local riverine ratios unaffected by exchange with seawater, whereas sites beneath well‐mixed seawater will preserve global flux signatures.

A decade of global volcanic SO2 emissions measured from space

The global flux of sulfur dioxide (SO2) emitted by passive volcanic degassing is a key parameter that constrains the fluxes of other volcanic gases (including carbon dioxide, CO2) and toxic trace metals (e.g., mercury). It is also a required input for atmospheric chemistry and climate models, since it impacts the tropospheric burden of sulfate aerosol, a major climate-forcing species. Despite its significance, an inventory of passive volcanic degassing is very difficult to produce, due largely to the patchy spatial and temporal coverage of ground-based SO2 measurements. We report here the first volcanic SO2 emissions inventory derived from global, coincident satellite measurements, made by the Ozone Monitoring Instrument (OMI) on NASA’s Aura satellite in 2005–2015. The OMI measurements permit estimation of SO2 emissions from over 90 volcanoes, including new constraints on fluxes from Indonesia, Papua New Guinea, the Aleutian Islands, the Kuril Islands and Kamchatka. On average over the past decade, the volcanic SO2 sources consistently detected from space have discharged a total of ~63 kt/day SO2 during passive degassing, or ~23 ± 2 Tg/yr. We find that ~30% of the sources show significant decadal trends in SO2 emissions, with positive trends observed at multiple volcanoes in some regions including Vanuatu, southern Japan, Peru and Chile.

Geochemical characteristics, speciation and size-fractionation of iron (Fe) in two marine shallow-water hydrothermal systems, Dominica, Lesser Antilles

Marine shallow-water hydrothermal systems have so far largely been neglected with respect to trace metal fluxes and possible stabilizing complexation processes, even though they emit their fluids directly into the photic zone. The impact of stabilized dissolved metal input by shallow vents into surface waters as well as the effect on the transport and bioavailability of bioactive trace metals within the area of highest primary production rates in the world oceans is therefore, at present, mostly unknown.In this study, we investigated the concentration, size fraction distribution (colloidal and soluble) as well as redox speciation and labile concentrations of the limiting micronutrient iron (Fe) at two marine shallow-water hydrothermal systems (Champagne Hot Springs and Soufriere) off the coast of Dominica, Lesser Antilles Island Arc, Caribbean.Geochemical characterization of the two different vent sites showed that both are affected by meteoric and seawater influence, with a stronger meteoric influence at Soufriere than at Champagne Hot Springs. Measurements of soluble and labile Fe were performed using a modified competitive ligand exchange – adsorptive cathodic stripping voltammetry (CLE-AdCSV) with salicylaldoxime (SA) as the artificial ligand. Our results show that focused fluids discharging at the seafloor, as well as hydrothermal pore fluids are, despite a calculated theoretical oxidation half-life of only 6.4min, highly enriched in Fe(II), indicating a strong complexation of Fe(II), strong enough to prevent Fe(II) from oxidation and precipitation. Since these fluids show enriched dissolved organic carbon (DOC) concentrations, and very low fractions of chemically labile Fe, complexation may occur by organic carbon, which was recently suggested to also be a factor in stabilizing particulate Fe(II) in deep-sea hydrothermal non-buoyant plumes.Our results indicate that shallow-water hydrothermalism off the coast of Dominica releases high concentrations of stabilized, bioavailable Fe(II) into the photic zone, which influences the biogeochemical cycle of Fe in surface waters. Considering the abundance of marine shallow-water hydrothermal systems in many regions, such processes may even play a role in the global oceanic dFe cycle.

Application of 224Ra and 222Rn for evaluating seawater residence times in a tidal subterranean estuary

The length of time in which seawater circulates through the beach face and mixes with terrestrial groundwater will have a profound influence on the geochemical cycling of nutrient deliveries to surface waters through submarine groundwater discharge. The goal of this work is to utilize pore water measurements of 222Rn and Ra isotopes to evaluate the time-scale of tidal seawater circulation in a coastal bluff and a barrier beach subterranean estuary (STE) on Long Island, NY. Intertidal pore water profiles sampled monthly between 2014 and 2015 revealed distinct geochemical differences between the two sites that were driven by the primary hydrogeologic forcing mechanisms. The coastal bluff site was dominated by a large hydraulic gradient that drove terrestrial groundwater discharge, while the barrier beach site had saline pore waters and was physically controlled by tidal forcing mechanisms. These mechanisms resulted in notably different pore water radionuclide (222Rn, 223,224,226,228Ra) and trace metal (Fe, Mn, Ba) distributions in the STE. A one-dimensional advective transport model was applied to estimate the residence time of circulated seawater within the STE using measured radionuclide activities. There are inherent uncertainties within the model, set by the activity of deep groundwater that has mixed with the circulated seawater, the initial activity of seawater that infiltrated the coastal aquifer and the radionuclide production rates. Residence times generally increased with depth from 0.1 to ≥15d and were greater in the low tide well of the barrier beach (4.9±3.4d) compared to the coastal bluff (1.1±0.4d). Residence times were fairly constant over time within the coastal bluff STE but varied seasonally in the barrier beach STE, suggesting that the barrier beach may have not been in “steady-state.” Variable pore water residence times within the STE may have a profound effect on the cycling of carbon, nutrient and trace metal fluxes to the coastal ocean.

Influence of Anthropogenic Activities on Trace Metal Accumulation in Brazilian Mangrove Sediments

Two sediment cores were collected at the margins of well-developed mangrove forests to study the effects of anthropogenic activities in the Paranagua region of Brazil. Calculations of sediment trace metal content, flux, and enrichment factors (EF) were performed. Trace metal (Hg, Zn, Pb, Ni, Co, Mn and Cu) contents showed differing values down core and amongst sites, which were not indicative of metal accumulation rates or EF. Slight enrichments of these metals were observed congruent with mining activities in the area occurring prior to 1900. Multiple rapid increases of flux rates were observed, one congruent with pre-industrial mining activity which was observed in both sediment cores. The other flux spike was only detected in one sediment core, occurring post 1990, and was not accompanied by any enrichment. This increase in flux is believed to be due to upstream urban development causing increased fine grain particle deposition in the mangroves of Laranjeiras Bay. Beyond assessing impacts of anthropogenic activities on mangroves of this area, an additional focal point of this work is to show the significance of content flux and EF in studies concerning coastal sediment pollution research. The validity of using flux and EF data, in addition to metals contents, to discern contamination trends in mangrove sediments is discussed.

Dissolved trace metals in low-order, urban stream water, Columbus, Ohio

Urban areas are thought to possess different geochemical characteristics than more natural regions due to large human population densities and intensified human activities that produce large quantities of waste products. In this work we have analyzed a number of urban streams in Columbus, Ohio, the 15th largest city in the U.S., for their dissolved trace metal concentrations. The three streams have subtle but measurably different land use patterns. Although, in general, the dissolved metal values observed are higher than global average river concentrations, there were no statistically different values between the streams. This suggests that urbanization may help to homogenize trace metal sources and fluxes, even on the small watershed scale, or that dissolved trace metals are not a variable that can be discriminated by land use subtype.

Cycling of redox-sensitive elements in a sandy subterranean estuary of the southern North Sea

The cycling of metals and sulfur plays an important role in beach sediments. We studied the redox-sensitive metals Mn, Fe, U, Re, Mo, and V, in relation to salinity, organic matter-, and sulfur cycling within the subterranean estuary of a barrier island sand beach on Spiekeroog Island, Northern Germany. Pore water samples were obtained along a cross-shore transect down to 5m below the sediment surface.Redox conditions range from oxic, close to the base of the dune, to sub- to anoxic towards the low water line. We demonstrate that biogeochemical processes alter not only the pore water concentrations of the trace metals, but are also reflected by the O isotope- and to a minor degree the S isotope composition of dissolved SO42−. The deviations from conservative mixing between terrestrial and marine endmembers influence trace metal fluxes into the ocean via submarine groundwater discharge. Redox reactions may be accelerated by the presence of dissolved reactive Mn, which we detected in shallow suboxic pore waters. Changes in the O isotope composition of SO42− indicate a cryptic S cycle in the suboxic zone that is fueled by the cycling of Fe and Mn.Seawater circulation through sediments of the upper beach (duneward part of the intertidal zone) removes U and V from solution, but serves as a source for Mn, Fe, Re, and Mo to the ocean. Pore water discharging from a berm close to the low water line exhibits lower U, V, and Re concentrations than adjacent seawater. This part of the beach thus serves as a sink for U, V, and Re, but as a source for Mn, Fe, and Mo. No significant Mo depletion is found in the pore water, due to the lack of dissolved sulfide. Net flux rates from the subterranean estuary into the ocean are estimated to be 185mmol for Fe, 48mmol for Mn, 8.3μmol for Mo, −24.7nmol for Re, −8.6μmol for U, and −24μmol for V per day and meter of shore line. These fluxes include freshwater flux from the island's freshwater lens and seawater circulation through the beach face. The subterranean estuary therefore serves as V, U, and Re sink, but as a source for Fe, Mn, and Mo to adjacent seawater.A first comparison of net fluxes of dissolved metals from the Spiekeroog beach system with the island's backbarrier tidal flat margins indicates that the tidal flat area might be of greater importance for the supply or removal of metals to/from the North Sea.

Fluxes of nutrients and trace metals across the sediment-water interface controlled by sediment-capping agents: bentonite and sand.

The effect of bentonite and sand, as natural capping agents, on the fluxes of nutrients and trace metals across the sediment-water interface was studied through sediment incubation, and the ecotoxicological impact was assessed by using Daphnia magna. Bentonite and sand were layered on the sediment at 15, 75, and 225mgcm(-2), and the concentration of cations, nutrients, and trace metals was measured. Sediment incubation showed that bentonite reduced the N flux but increased the P flux as a result of dissolution of non-crystalline P from bentonite, while sand slightly decreased the N fluxes but not the P flux. The concentration of Na increased in the overlying water with increasing application rates of bentonite, while that of Ca decreased. However, regardless of the rate of sand application, concentrations of all cation species remained unchanged. The concentration of As and Cr increased with bentonite application rate but decreased with sand. Both capping materials suppressed fluxes of Cd, Cu, Ni, and Zn compared to control, and the extent of suppression was different depending on the trace metal species and capping agents used. During sediment incubation, the survival rate of D. magna significantly decreased in bentonite suspension but began to decrease at the end in sand suspension. Sediment capping of mildly polluted sediments by using bentonite and sand lowered the level of nutrients and trace metals. However, unexpected or undesirable side effects, such as influxes of P and As from bentonite to the overlying water and a possibility of toxic impacts to aquatic ecosystems, were observed, suggesting that capping agents with an adequate assessment of their side effects and toxicity should be predetermined for site-specific sediment management strategies.