Iron colloids dominate sedimentary supply to the ocean interior

Dissolution of marine sediment is a key source of dissolved iron (Fe) that regulates the ocean carbon cycle. Currently, our prevailing understanding, encapsulated in ocean models, focuses on low-oxygen reductive supply mechanisms and neglects the emerging evidence from iron isotopes in seawater and sediment porewaters for additional nonreductive dissolution processes. Here, we combine measurements of Fe colloids and dissolved δ56Fe in shallow porewaters spanning the full depth of the South Atlantic Ocean to demonstrate that it is lithogenic colloid production that fuels sedimentary iron supply away from low-oxygen systems. Iron colloids are ubiquitous in these oxic ocean sediment porewaters and account for the lithogenic isotope signature of dissolved Fe (δ56Fe = +0.07 ± 0.07‰) within and between ocean basins. Isotope model experiments demonstrate that only lithogenic weathering in both oxic and nitrogenous zones, rather than precipitation or ligand complexation of reduced Fe species, can account for the production of these porewater Fe colloids. The broader covariance between colloidal Fe and organic carbon (OC) abundance suggests that sorption of OC may control the nanoscale stability of Fe minerals by inhibiting the loss of Fe(oxyhydr)oxides to more crystalline minerals in the sediment. Oxic ocean sediments can therefore generate a large exchangeable reservoir of organo-mineral Fe colloids at the sediment water interface (a “rusty source”) that dominates the benthic supply of dissolved Fe to the ocean interior, alongside reductive supply pathways from shallower continental margins.

Accumulation of Methylmercury in the High-Altitude Lake Uru Uru (3686 m a.s.l, Bolivia) Controlled by Sediment Efflux and Photodegradation

In shallow aquatic environments, sediment is a significant source of monomethylmercury (MMHg) for surface water (SW). High-altitude aquatic ecosystems are characterized by extreme hydro-climatic constraints (e.g., low oxygen and high UV radiation). We studied, during two seasons, the diel cycles of MMHg in SW and sediment porewaters (PW) of Lake Uru Uru (3686 m a.s.l, Bolivia) contaminated by urban and mining activities. Our results show that diel changes in SW MMHg concentrations (up to 1.8 ng L−1) overwhelm seasonal ones, with higher MMHg accumulation during the night-time and the dry season. The calculation of MMHg diffusive fluxes demonstrates that the sediment compartment was the primary source of MMHg to the SW. Most MMHg efflux occurred during the dry season (35.7 ± 17.4 ng m−2 day−1), when the lake was relatively shallow, more eutrophicated, and with the redoxcline located above the sediment–water interface (SWI). Changes in MMHg accumulation in the PWs were attributed to diel redox oscillations around the SWI driving both the bacterial sulfate reduction and bio-methylation. Finally, we highlight that although MMHg loading from the PW to the SW is large, MMHg photodegradation and demethylation by microorganisms control the net MMHg accumulation in the water column.

Water Column Turbidity Not Sediment Nutrient Enrichment Moderates Microphytobenthic Primary Production

Soft sediment intertidal habitats are under intense anthropogenic pressure resulting from increased land derived sediment and nutrient delivery. Long term, this can cause high water column turbidity and nutrient enrichment of sediment porewaters, which has cascading effects on coastal ecosystem functionality. However, how these stressors may interact and influence benthic productivity over alternating periods of submergence and emergence is largely unknown. This study investigates the effects of sediment nutrient enrichment (at three levels for 20 months) on benthic primary production at six sites in four New Zealand estuaries that spanned a gradient in water column turbidity. While nutrient enrichment had no detectable effect on microphytobenthic primary production, water column turbidity had a significant influence, explaining up to 40% of variability during tidal submergence, followed by temperature and sediment characteristics. In addition, negative net primary production (NPP) estimates and therefore net heterotrophy for the most turbid estuaries during tidal submergence resulted in an increased reliance on production during emerged periods, where NPP was positive across all sites. This study highlights the prominent role of water column turbidity over nutrient enrichment in moderating microphytobenthic production, and the increasing importance of emerged periods to maintain the health and functioning of coastal habitats.

Carbonate chemistry in sediment porewaters of the Rhône River delta driven by early diagenesis (northwestern Mediterranean)

The Rhône River is the largest source of terrestrial organic and inorganic carbon for the Mediterranean Sea. A large fraction of this terrestrial carbon is either buried or mineralized in the sediments close to the river mouth. This mineralization follows aerobic and anaerobic pathways, with a range of impacts on calcium carbonate precipitation and dissolution in the sediment near the sediment–water interface. This study focuses on the production of dissolved inorganic carbon (DIC) and total alkalinity (TA) by early diagenesis, consequential pH variations and the effect on calcium carbonate precipitation or dissolution. The sediment porewater chemistry was investigated along a transect from the Rhône River outlet to the continental shelf. TA and concentrations of DIC, SO42− and Ca2+ were analyzed on bottom waters and extracted sediment porewaters, whereas pH and oxygen concentrations were measured in situ using microelectrodes. The average oxygen penetration depth into the sediment was 1.7 ± 0.4 mm close to the river mouth and 8.2 ± 2.6 mm in the continental shelf sediments, indicating intense respiration rates. Diffusive oxygen fluxes through the sediment–water interface ranged between 3 and 13 mmol O2 m−2 d−1. In the first 30 cm of the sediment, TA and DIC porewater concentrations increased with depth up to 48 mmol L−1 near the river outlet and up to 7 mmol L−1 on the shelf as a result of aerobic and anaerobic mineralization processes. Due to aerobic processes, at all stations pH decreased by 0.6 pH units in the oxic layer of the sediment accompanied by a decrease of the saturation state regarding calcium carbonate. In the anoxic layer of the sediments, sulfate reduction was the dominant mineralization process and was associated with an increase of porewater saturation state regarding calcium carbonate. Ultimately anoxic mineralization of organic matter caused calcium carbonate precipitation demonstrated by a large decrease in Ca2+ concentration with depth in the sediment. Carbonate precipitation decreased in the offshore direction, together with the carbon turnover and sulfate consumption in the sediments. The large production of porewater alkalinity characterizes these sediments as an alkalinity source to the water column, which may increase the CO2 buffering capacity of these coastal waters. Estuarine sediments should therefore receive more attention in future estimations of global carbon fluxes.

In situ speciation of dissolved inorganic antimony in surface waters and sediment porewaters: development of a thiol-based diffusive gradients in thin films technique for SbIII

A new in situ sampling method enables the selective measurement of Sb(iii) in surface waters and sediment porewaters.

Benthic fluxes of dissolved organic nitrogen in the lower St. Lawrence estuary and implications for selective organic matter degradation

The distribution of dissolved organic nitrogen (DON) and carbon (DOC) in sediment porewaters was determined at nine locations along the St. Lawrence estuary and in the gulf of St. Lawrence. In a previous manuscript (Alkhatib et al., 2012a), we have shown that this study area is characterized by gradients in the sedimentary particulate organic matter (POM) reactivity, bottom water oxygen concentrations, and benthic respiration rates. Based on the porewater profiles, we estimated the benthic diffusive fluxes of DON and DOC in the same area. Our results show that DON fluxed out of the sediments at significant rates (110 to 430 μmol m−2 d−1). DON fluxes were positively correlated with sedimentary POM reactivity and varied inversely with sediment oxygen exposure time (OET), suggesting direct links between POM quality, aerobic remineralization and the release of DON to the water column. DON fluxes were on the order of 30 to 64% of the total benthic inorganic fixed N loss due to denitrification, and often exceeded the diffusive nitrate fluxes into the sediments. Hence they represented a large fraction of the total benthic N exchange, a result that is particularly important in light of the fact that DON fluxes are usually not accounted for in estuarine and coastal zone nutrient budgets. In contrast to DON, DOC fluxes out of the sediments did not show any significant spatial variation along the Laurentian Channel (LC) between the estuary and the gulf (2100 ± 100 μmol m−2 d−1). The molar C / N ratio of dissolved organic matter (DOM) in porewater and the overlying bottom water varied significantly along the transect, with lowest C / N in the lower estuary (5–6) and highest C / N (> 10) in the gulf. Large differences between the C / N ratios of porewater DOM and POM are mainly attributed to a combination of selective POM hydrolysis and elemental fractionation during subsequent DOM mineralization, but selective adsorption of DOM to mineral phases could not be excluded as a potential C / N fractionating process. The extent of this C- versus N- element partitioning seems to be linked to POM reactivity and redox conditions in the sediment porewaters. Our results thus highlight the variable effects selective organic matter (OM) preservation can have on bulk sedimentary C / N ratios, decoupling the primary source C / N signatures from those in sedimentary paleoenvironmental archives. Our study further underscores that the role of estuarine sediments as efficient sinks of bioavailable nitrogen is strongly influenced by the release of DON during early diagenetic reactions, and that DON fluxes from continental margin sediments represent an important internal source of N to the ocean.