-
Evaluation of the migration of 15 photo-initiators from cardboard packaging into Tenax® using ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS)
-
Photo-initiators are widely used to cure ink on packaging materials used in food applications such as plastic films or cartonboards. In migration studies, food simulants are very often used to simulate food, like Tenax®, which is the simulant for dry foodstuffs. In this paper a fast and reliable confirmation method for the determination of the following photoinitiators in Tenax® is described: benzophenone (BP), 4,4´-bis(diethylamino)benzophenone (DEAB), 2-chloro-9H-thioxanthen-9-one (CTX), 1-chloro-4-propoxy-9H-thioxanthen-9-one (CPTX), 2,4-diethyl-9H-thioxanthen-9-one(DETX), 2,2-dimethoxy-2-phenyl acetophenone (DMPA), 4-(dimethylamino)benzophenone (DMBP), 2-ethylanthraquinone(EA), ethyl-4-dimethylaminobenzoate (EDMAB), 1-hydroxylcyclohexyl phenyl ketone (HCPK), 2-hydroxy-4´- (2-hydroxyethoxy)-2-methylpropiophenone (HMMP), 2-isopropyl-9H-thioxanthen-9-one (ITX), 4-methylbenzophenone(MBP), Michler’s ketone (MK), and 4-phenylbenzophenone (PBZ). After the migration study was completed, the simulant Tenax® was extracted using acetonitrile, followed by analysis on ultra-performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS). Quantification was carried out using benzophenone-d10 (BP-d10) as internal standard. The presented method is validated in terms of matrix effect, specificity, linearity, recovery, precision and sensitivity, showing the method can detect all photo-initiators at very low concentrations (LOD < 0.125 μg g–1 for all substances). Finally, the procedure was applied to real samples, proving the capabilities of the presented method.
Located in
Library
/
No RBINS Staff publications
-
The impact of electrogenic sulfur oxidation on the biogeochemistry of coastal sediments: A field study
-
Electro-active sediments distinguish themselves from other sedimentary environments by the presence of microbially induced electrical currents in the surface layer of the sediment. The electron transport is generated by metabolic activity of long filamentous cable bacteria, in a process referred to as electrogenic sulfur oxidation (e-SOx). Laboratory experiments have shown that e-SOx exerts a large impact on the sediment geochemistry, but its influence on the in situ geochemistry of marine sediments has not been previously investigated. Here, we document the biogeochemical cycling associated with e-SOx in a cohesive coastal sediment in the North Sea (Station 130, Belgian Coastal Zone) during three campaigns (January, March and May 2014). Fluorescence in situ hybridization showed that cable bacteria were present in high densities throughout the sampling period, and that filaments penetrated up to 7 cm deep in the sediment, which is substantially deeper than previously recorded. High resolution microsensor profiling (pH, H2S and O2) revealed the typical geochemical fingerprint of e-SOx, with a wide separation (up to 4.8 cm) between the depth of oxygen penetration and the depth of sulfide appearance. The metabolic activity of cable bacteria induced a current density of 25–32 mA m-2 and created an electrical field of 12–17 mV m-1 in the upper centimeters of the sediment. This electrical field created an ionic drift, which strongly affected the depth profiles and fluxes of major cations (Ca2+, Fe2+) and anions (SO42-) in the pore water. The strong acidification of the pore water at depth resulted in the dissolution of calcium carbonates and iron sulfides, thus leading to a strong accumulation of iron, calcium and manganese in the pore water. While sulfate accumulated in the upper centimeters, no significant effect of e-SOx was found on ammonium, phosphate and silicate depth profiles. Overall, our results demonstrate that cable bacteria can strongly modulate the sedimentary biogeochemical cycling under in situ conditions
Located in
Library
/
No RBINS Staff publications
-
The Influence of Bioturbation on Iron and Sulphur Cycling in Marine Sediments: A Model Analysis
-
The geochemical cycles of iron and sulphur in marine sediments are strongly intertwined and give rise to a complex network of redox and precipitation reactions. Bioturbation refers to all modes of transport of particles and solutes induced by larger organisms, and in the present-day seafloor, bioturbation is one of the most important factors controlling the biogeochemical cycling of iron and sulphur. To better understand how bioturbation controls Fe and S cycling, we developed reactive transport model of a coastal sediment impacted by faunal activity. Subsequently, we performed a model sensitivity analysis, separately investigating the two different transport modes of bioturbation, i.e. bio-mixing (solid particle transport) and bio-irrigation (enhanced solute transport). This analysis reveals that bio-mixing and bio-irrigation have distinct—and largely opposing effects on both the iron and sulphur cycles. Bio-mixing enhances transport between the oxic and suboxic zones, thus promoting the reduction of oxidised species (e.g. iron oxyhydroxides) and the oxidation of reduced species (e.g. iron sulphides). Through the reoxidation of iron sulphides, bio-mixing strongly enhances the recycling of Fe and S between their reduced and oxidised states. Bio-irrigation on the other hand removes reduced solutes, i.e. ferrous iron and free sulphide, from the sediment pore water. These reduced species are then reoxidised in the overlying water and not recycled within the sediment column, which leads to a decrease in Fe and S recycling. Overall, our results demonstrate that the ecology of the macrofauna (inducing bio-mixing or bio-irrigation, or both) matters when assessing their impact on sediment geochemistry. This finding seems particularly relevant for sedimentary cycling across Cambrian transition, when benthic fauna started colonizing and reworking the seafloor.
Located in
Library
/
No RBINS Staff publications
-
Influence of Natural Oxygenation of Baltic Proper Deep Water on Benthic Recycling and Removal of Phosphorus, Nitrogen, Silicon and Carbon
-
At the end of 2014, a Major Baltic Inflow (MBI) brought oxygenated, salty water into the Baltic proper and reached the long-term anoxic Eastern Gotland Basin (EGB) by March 2015. In July 2015, we measured benthic fluxes of phosphorus (P), nitrogen (N) and silicon (Si) nutrients and dissolved inorganic carbon (DIC) in situ using an autonomous benthic lander at deep sites (170–210 m) in the EGB, where the bottom water oxygen concentration was 30–45 μM. The same in situ methodology was used to measure benthic fluxes at the same sites in 2008–2010, but then under anoxic conditions. The high efflux of phosphate under anoxic conditions became lower upon oxygenation, and turned into an influx in about 50% of the flux measurements. The C:P and N:P ratios of the benthic solute flux changed from clearly below the Redfield ratio (on average about 70 and 3–4, respectively) under anoxia to approaching or being well above the Redfield ratio upon oxygenation. These observations demonstrate retention of P in newly oxygenated sediments. We found no significant effect of oxygenation on the benthic ammonium, silicate and DIC flux. We also measured benthic denitrification, anammox, and dissimilatory nitrate reduction to ammonium (DNRA) rates at the same sites using isotope-pairing techniques. The bottom water of the long-term anoxic EGB contained less than 0.5 μM nitrate in 2008–2010, but the oxygenation event created bottom water nitrate concentrations of about 10 μM in July 2015 and the benthic flux of nitrate was consistently directed into the sediment. Nitrate reduction to both dinitrogen gas (denitrification) and ammonium (DNRA) was initiated in the newly oxygenated sediments, while anammox activity was negligible. We estimated the influence of this oxygenation event on the magnitudes of the integrated benthic P flux (the internal P load) and the fixed N removal through benthic and pelagic denitrification by comparing with a hypothetical scenario without the MBI. Our calculations suggest that the oxygenation triggered by the MBI in July 2015, extrapolated to the basin-wide scale of the Baltic proper, decreased the internal P load by 23% and increased the total (benthic plus pelagic) denitrification by 18%.
Located in
Library
/
No RBINS Staff publications
-
Comparison of Chelex based resins in diffusive gradients in thin-film for high resolution assessment of metals
-
The passive sampling technique of diffusive gradients in thin-film (DGT) is widely used to determine 1D profiles (using Chelex-100 resin) and 2D images (using suspended particulate reagent-iminodiacetate resin, abbreviated as SPR-IDA resin) of metals in sediment pore waters and in oxic/anoxic soils. However, when deployed in anoxic sediments with high metal concentrations, Fe and Mn concentrations determined with the Chelex-100 resin gel were ~ 5 times higher than concentrations measured with the SPR-IDA resin gel. This discrepancy suggests that the SPR-IDA resin gel is saturated faster than the Chelex-100 resin gel. Here, we tested the adsorption capacity of the SPR-IDA resin gel and compared it to the Chelex-100 resin gel. Fe and Mn binding capacities on a SPR-IDA gel disc are less than 0.1 μmoles, which means that they are far below those on a Chelex-100 gel disc (around 3.2 μmoles), while competition with stronger binding metals such as Cu and Cd further lowers Fe and Mn capacities. This restricts the SPR-IDA resin gel to be used in contaminated marine sediments. We propose the use of a ground Chelex-100 resin, which is prepared by grinding Chelex-100 resin in a ball-mill prior to gel preparation. The capacities of Fe and Mn on a ground Chelex-100 resin gel disc are around 1.6 μmoles, more than 16 times higher than the capacity on SPR-IDA gel disc. In addition, the bead size of the ground Chelex-100 resin is small enough (~ 10 μm) to allow high resolution LA-ICP-MS imaging of Fe, Mn and trace metals in sediment pore waters as well as soils.
Located in
Library
/
No RBINS Staff publications
-
Transient bottom water oxygenation creates a niche for cable bacteria in long-term anoxic sediments of the Eastern Gotland Basin
-
Cable bacteria have been reported in sediments from marine and freshwater locations, but the environmental factors that regulate their growth in natural settings are not well understood. Most prominently, the physiological limit of cable bacteria in terms of oxygen availability remains poorly constrained. In this study, we investigated the presence, activity and diversity of cable bacteria in relation to a natural gradient in bottom water oxygenation in a depth transect of the Eastern Gotland Basin (Baltic Sea). Cable bacteria were identified by FISH at the oxic and transiently oxic sites, but not at the permanently anoxic site. Three species of the candidate genus Electrothrix, i.e. marina, aarhusiensis and communis were found coexisting within one site. The highest filament density (33 m cm−2) was associated with a 6.3 mm wide zone depleted in both oxygen and free sulphide, and the presence of an electric field resulting from the electrogenic sulphur oxidizing metabolism of cable bacteria. However, the measured filament densities and metabolic activities remained low overall, suggesting a limited impact of cable bacteria at the basin level. The observed bottom water oxygen levels (< 5 μM) are the lowest so far reported for cable bacteria, thus expanding their known environmental distribution.
Located in
Library
/
No RBINS Staff publications
-
Early Palaeozoic ocean anoxia and global warming driven by the evolution of shallow burrowing
-
The evolution of burrowing animals forms a defining event in the history of the Earth. It has been hypothesised that the expansion of seafloor burrowing during the Palaeozoic altered the biogeochemistry of the oceans and atmosphere. However, whilst potential impacts of bioturbation on the individual phosphorus, oxygen and sulphur cycles have been considered, combined effects have not been investigated, leading to major uncertainty over the timing and magnitude of the Earth system response to the evolution of bioturbation. Here we integrate the evolution of bioturbation into the COPSE model of global biogeochemical cycling, and compare quantitative model predictions to multiple geochemical proxies. Our results suggest that the advent of shallow burrowing in the early Cambrian contributed to a global low-oxygen state, which prevailed for ~100 million years. This impact of bioturbation on global biogeochemistry likely affected animal evolution through expanded ocean anoxia, high atmospheric CO2 levels and global warming.
Located in
Library
/
No RBINS Staff publications
-
Carbon, iron and sulphur cycling in the sediments of a Mediterranean lagoon (Ghar El Melh, Tunisia)
-
Coastal lagoon sediments are important for the biogeochemical carbon cycle at the land-ocean transition, as they form hotspots for organic carbon burial, as well as potential sites for authigenic carbonate formation. Here, we employ an early diagenetic model to quantify the coupled redox cycling of carbon, iron and sulphur in the sediments of the shallow Ghar El Melh (GEM) lagoon (Tunisia). The model simulated depth profiles show a good correspondence with available pore water data (dissolved inorganic carbon, NH4+, total alkalinity, Ca2+, Fe2+ and SO42−) and solid phase data (organic matter, pyrite, calcium carbonate and iron (oxyhydr)oxides). This indicates that the model is able to capture the dominant processes influencing the sedimentary biogeochemical cycling. Our results show that sediment of the GEM lagoon is an efficient reactor for organic matter breakdown (burial efficiency < 10%), with an important role for aerobic respiration (32%) and sulphate reduction (61%). Despite high rates of sulphate reduction, free sulphide does not accumulate in the pore water, due to a large terrestrial input of reactive iron oxides and the efficient sequestration of free sulphide into iron sulphide phases. High pyrite burial (2.2 mmol FeS2 m−2 d−1) prevents the reoxidation of reduced sulphide, thus resulting in a low total oxygen uptake (4.7 mmol m−2 d−1) of the sediment and a relatively high oxygen penetration depth. The formation of pyrite also generates high amounts of alkalinity in the pore water, which stimulates authigenic carbonate precipitation (2.7 mmol m−2 d−1) and leads to alkalinity release to the overlying water (3.4 mmol m−2 d−1). Model simulations with and without an N-cycle reveal a limited influence of nitrification and denitrification on overall organic matter diagenesis. Overall, our study highlights the potential role of coastal lagoons for the global carbon and sulphur cycle, and their possible contribution to shelf alkalinity, which increases the buffering capacity of the coastal ocean for CO2 uptake.
Located in
Library
/
No RBINS Staff publications
-
Elevated sedimentary removal of Fe, Mn, and trace elements following a transient oxygenation event in the Eastern Gotland Basin, central Baltic Sea
-
Iron, manganese, and trace elements play an important role in the marine carbon cycle as they are limiting nutrients for marine primary productivity. Water column concentrations of these bio-essential elements are controlled by the balance between input and removal, with burial in marine sediments being the main sink. The efficiency of this burial sink is dependent on the redox state of the water column, with sediments underlying a sulphidic (euxinic) water column being the most efficient sinks for Fe, but also Mn and trace elements (Co, Cd, Ni, Mo, As, W, V, and U). Transient changes in ocean redox state can hence affect trace element burial, and correspondingly, the ocean’s trace element inventory, but the impact of transient oxygenation events on trace element cycling is currently not well understood. Here, we investigate the impact of a natural oxygenation event on trace element release and burial in sediments of the Eastern Gotland Basin (EGB), a sub-basin of the Baltic Sea. After being anoxic (<0.5 mMO2) for ~10 years, the deep waters of the EGB experienced a natural oxygenation event (Major Baltic Inflow, MBI) in 2015. Following this oxygenation event, we deployed benthic chamber landers along a depth transect in the EGB in April 2016, 2017 and 2018. We complemented these in situ flux measurements with analyses of water column, solid phase and pore water chemistry. Overall, the event increased the benthic effluxes of dissolved trace elements, though particular responses were element-specific and were caused by different mechanisms. Enhanced fluxes of Cd and U were caused by oxidative remobilisation, while Ni showed little response to the inflow of oxygen. In contrast, enhanced release of Co, Mo, As, W, and V was caused by the enhanced transient input of Mn oxides into the sediment, whereas Fe oxides were of minor importance. Following the dissolution of the oxides in the sediment, Mn and W were nearly completely recycled back to the water column, while fractions of Fe, Co, Mo, As, and V were retained in the sediment. Our results suggest that transient oxygenation events in euxinic basins may decrease the water column inventory of certain trace elements (Fe, Co, Mo, As, and V), thus potentially affecting global marine primary productivity on longer timescales.
Located in
Library
/
No RBINS Staff publications
-
Burrowing fauna mediate alternative stable states in the redox cycling of salt marsh sediments
-
The East Anglian salt marsh system (UK) has recently generated intriguing data with respect to sediment biogeochemistry. Neighbouring ponds in these salt marshes show two distinct regimes of redox cycling: the sediments are either iron-rich and bioturbated, or they are sulphide-rich and unbioturbated. No conclusive explanation has yet been given for this remarkable spatial co-occurrence. Here, we quantify the geochemical cycling in both pond types, using pore-water analyses and solid-phase speciation. Our results demonstrate that differences in solid-phase carbon and iron inputs are likely small between pond types, and so these cannot act as the direct driver of the observed redox dichotomy. Instead, our results suggest that the presence of bioturbation plays a key role in the transition from sulphur-dominated to iron-dominated sediments. The presence of burrowing fauna in marine sediments stimulates the mineralisation of organic matter, increases the iron cycling and limits the build-up of free sulphide. Overall, we propose that the observed dichotomy in pond geochemistry is due to alternative stable states, which result from non-linear interactions in the sedimentary iron and sulphur cycles that are amplified by bioturbation. This way, small differences in solid phase input can result in very different regimes of redox cycling due to positive feedbacks. This non-linearity in the iron and sulphur cycling could be an inherent feature of marine sediments, and hence, alternative stable states could be present in other systems.
Located in
Library
/
No RBINS Staff publications
