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Antarctic ice cores reveal a glacial climate state during Marine Isotope Stage 3 (MIS‐3; 57–29 ka) punctuated by millennial‐scale warming events and pulses of CO2. This study further explores how changes in Southern Ocean carbon cycling contributed to these millennial‐scale fluctuations in climate. Evidence from South Atlantic sediment cores suggests that warming events were associated with decreased dust‐borne iron flux, reduced export production, and increased upwelling from the deep Southern Ocean (SO). These processes are considered to have contributed to rising atmospheric CO2 during periods of rapid warming. Here we investigate whether the same processes occurred in the southwest Pacific sector of the SO at TAN1106‐28. We show that reduced New Zealand glaciation and localized iron limitation in the southwest Pacific led to reduced export production during millennial‐scale warming events. Decreases in foraminifera‐bound δ15N during all MIS‐3 warming events may reflect increased nutrient supply by upwelling. Increased calcium carbonate flux during MIS‐3 warming events likely reflects coccolithophore production in response to sea surface temperatures, which, would increase carbonate counter pump strength and reduce CO2 sequestration. Concomitant decreases in bottom water oxygen, inferred from redox‐sensitive U and Mn sediment concentrations, and increases in the 14C age of deep waters, suggest that old, nutrient‐rich waters influenced southwest Pacific middepth waters during warming events. This signature may reflect an expansion of Pacific Deep Water into the SO during warming. Taken together, our multi‐proxy data set reveals that the southwest subantarctic Pacific acted as a source of CO2 during millennial‐scale warming events of MIS‐3. Plain Language Summary: Antarctic ice cores have provided evidence of episodes of warming and cooling of the Southern Hemisphere that took place over hundreds to thousands of years between 57,000 and 29,000 years ago. During warming events, the Southern Ocean is thought to have played a role in the increasing concentration of CO2 in the atmosphere. Here we use a sediment core from the southwest Pacific Southern Ocean to show that decreased iron input to the surface ocean reduced biological productivity during warming events, which hampered CO2 sequestration in the region. While in the deep ocean, proxies for the concentration of oxygen and the relative age of deep waters suggest that conditions may have become favorable for a release of CO2 from the ocean interior to the atmosphere during episodic warming. These findings support the theory that the Southern Ocean played an important role in the past carbon cycle by modulating the exchange of CO2 between the deep ocean and the atmosphere during periods of rapid climate change. Key Points: Decreased iron from New Zealand limits subantarctic Pacific export production during MIS‐3 warming eventsDecreases in foraminifera bound‐δ15N during MIS‐3 warming events are likely due to increased nutrient supply and reduced utilisationDecreases in bottom water O2 during MIS‐3 warming events may result from increased Pacific Deep Water influence [ABSTRACT FROM AUTHOR]

Copper is used extensively in semiconductor circuits as the multilayer metal. In addition to copper, waste streams often contain chelating agents like EDTA, which is widely used in the process to enhance solubility of copper, and it tends to form copper-chelated complexes. PEI-agarose adsorbents in a packed-bed column are capable of removing these anionic complexes, but the competitive binding between this chelating agent and PEI for copper is not well understood and needs to be explored.The currentworkfocuseson investigating copper sorption by PEI-agarose adsorbent in the presence of EDTA. The pH of the column is fixed at 5.5 using 0.1 M acetate buffer. The ratio of chelator to copper ions is varied. Copper binding capacity and copper breakthrough curves are compared and contrasted to results without additional chelator present An excess of EDTA leads to an increase in the fraction of free dissociated (anionic) ligand that competes for electrostatic attraction on protonated amine groups and therefore leads to a decrease in sorption capacity in the column. However, this waste treatment technique is still feasible for the semiconductor industry as large volumes of copper-contaminated solutions from actual waste can be concentrated 12-fold. When equimolar (copper to EDTA) or higher concentrations of EDTA are present, acetate can be utilized to recover the metal; for low ratios of copper to EDTA, metal recovery is achieved using hydrochloric acid. [ABSTRACT FROM AUTHOR]

The monosaccharide anhydrides levoglucosan, mannosan, and galactosan are known as 'fire sugars' as they are powerful proxies used to trace fire events. Despite their increasing use, their application is not completely understood, especially in the context of tracing past fire events using sediment samples. There are many uncertainties about fire sugar formation, partitioning, transport, complexation, and stability along all stages of the source-to-sink pathway. While these uncertainties exist, the efficacy of fire sugars as fire tracers remains limited. This study compared high-resolution fire sugar fluxes in freshwater sediment cores to known fire records in Tasmania, Australia. Past fire events correlated with fire sugar flux increases down-core, with the magnitude of the flux inversely proportional to the distance of the fires from the study site. For the first time, fire sugar ratios (levoglucosan/mannosan, L/M) in aerosols were compared with those in sediments from the same time-period. The L/M ratio in surface sediments (1.42-2.58) were significantly lower than in corresponding aerosols (5.08-15.62). We propose two hypotheses that may explain the lower average L/M of sediments. Firstly, the degradation rate of levoglucosan is higher than mannosan in the water column, sediment-water interface, and/or sediment. Secondly, the L/M ratio of non-atmospheric emissions during fires may be lower than that of atmospheric emissions from the same fire. Due to the uncertainties about transport partitioning (atmospheric versus non-atmospheric emissions) and fire sugar degradation along all stages of the source-to-sink pathway, we advise caution when inferring vegetation type (e.g. softwood, hardwood, or grasses) based purely on fire sugar ratios in sediments (e.g. L/M ratio). Future investigations are required to increase the efficacy of fire sugars as a complimentary, or standalone, fire tracer in sediments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Natural iron fertilization of the Southern Ocean by windblown dust has been suggested to enhance biological productivity and modulate the climate 1-3 . Yet, this process has never been quantified across the Southern Ocean and at annual timescales 4,5 . Here we combined 11 years of nitrate observations from autonomous biogeochemical ocean profiling floats with a Southern Hemisphere dust simulation to empirically derive the relationship between dust-iron deposition and annual net community production (ANCP) in the iron-limited Southern Ocean. Using this relationship, we determined the biological response to dust-iron in the pelagic perennially ice-free Southern Ocean at present and during the last glacial maximum (LGM). We estimate that dust-iron now supports 33% ± 15% of Southern Ocean ANCP. During the LGM, when dust deposition was 5-40-fold higher than today, the contribution of dust to Southern Ocean ANCP was much greater, estimated at 64% ± 13%. We provide quantitative evidence of basin-wide dust-iron fertilization of the Southern Ocean and the potential magnitude of its impact on glacial-interglacial timescales, supporting the idea of the important role of dust in the global carbon cycle and climate 6-8 ., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

The ability to trace current and past biomass burning events is important for understanding the links between human activity, fire frequency, and climate. One method of tracing biomass burning is to measure the concentrations of certain monosaccharides anhydrides (MAs), specifically levoglucosan (LEV) and its isomers, mannosan (MAN) and galactosan (GAL), which are products of cellulose and hemicellulose pyrolysis. This work presents a simple extraction method allowing for the rapid, sensitive, and selective determination of MAs in sediments. MAs detection was performed using suppressed ion chromatography with electrospray - triple-stage quadrupole tandem mass spectrometry (IC-TSQ-MS). The extraction method involves ultrasound probe sonication using water as the solvent. Extraction time, amplitude, and sonication mode were optimised. Recoveries higher than 86% for all MAs tested were achieved by applying 70% amplitude in continuous mode for 60 s. Analytical performance of the method included instrumental LODs of 0.10, 0.12 and 0.50 μg L -1 for LEV, MAN and GAL, respectively. No carryover issues, no matrix effect and no co-elution of targeted MAs with other sugars likely present in sediments samples were observed. The developed extraction method was further validated by the analysis of LEV and MAN in NIST® 1649b urban dust reference material and the resulting concentrations were in excellent agreement with previously reported values. MAs quantification in 70 lake sediment samples were carried out with concentrations found to range from 0.009 to 0.390 μg g -1 for LEV and from 0.009 to 0.194 μg g -1 for MAN. Plotting MAs concentrations versus approximate sediment age allowed the reconstruction of recent fire events impacting two locations in the Central Highlands of Tasmania, Australia.

Microplastics are ubiquitous in the marine environment and studies on their effects on benthic filter feeders at least partly revealed a negative influence. However, it is still unclear whether the effects of microplastics differ from those of natural suspended microparticles, which constitute a common stressor in many coastal environments. We present a series of experiments that compared the effects of six-week exposures of marine mussels to two types of natural particles (red clay and diatom shells) to two types of plastic particles (Polymethyl Methacrylate and Polyvinyl Chloride). Mussels of the family Mytilidae from temperate regions (Japan, Chile, Tasmania) through subtropical (Israel) to tropical environments (Cabo Verde) were exposed to concentrations of 1.5 mg/L, 15 mg/L and 150 mg/L of the respective microparticles. At the end of this period, we found significant effects of suspended particles on respiration rate, byssus production and condition index of the animals. There was no significant effect on clearance rate and survival. Surprisingly, we observed only small differences between the effects of the different types of particles, which suggests that the mussels were generally equally robust towards exposure to variable concentrations of suspended solids regardless of whether they were natural or plastic. We conclude, that microplastics and suspended solids elicit similar effects on the tested response variables, and that both types of microparticles mainly cause acute responses rather than more persistent carry-over effects., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 The Authors. Published by Elsevier B.V. All rights reserved.)

Understanding mechanistic pathways to radiolytic hydrogen generation by metal oxyhydroxide nanomaterials is challenging because of the difficulties of distinguishing key locations of OH bond scission, from structural interiors to hydroxylated surfaces to physi-sorbed water molecules. Here we exploited the interface-selectivity of vibrational sum frequency generation (VSFG) to isolate surface versus bulk hydroxyl groups for gibbsite and boehmite nanoplatelets before and after 60 Co irradiation at dose levels of approximately 7.0 and 29.6 Mrad. While high-resolution microscopy revealed no effect on particle bulk and surface structures, VSFG results clearly indicated up to 83% and 94% radiation-induced surface OH bond scission for gibbsite and boehmite, respectively, a substantially higher proportion than observed for interior OH groups by IR and Raman spectroscopy. Electron paramagnetic spectroscopy revealed that the major radiolysis products bound in the mineral structures are trapped electrons, O, O 2 - and possibly F-centers in gibbsite, and H, O and O 3 - in boehmite, which persist on the time frame of several months. The entrapped radiolysis products appear to be highly stable, enduring re-hydration of particle surfaces, and likely reflect a permanent adjustment in the thermodynamic stabilities of these nanomaterials., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Effects of microplastics on marine taxa have become a focal point in marine experimental biology. Almost all studies so far, however, assessed the influence of microplastics on animals only in relation to a zero-particle group. Documented microplastic impacts may thus be overestimated, since many marine species also experience natural suspended solids as a stressor. Here, we compared the effects of polyvinyl chloride (PVC) and red clay (mean for both particles: ~12-14 μm) on the Mediterranean mussel Mytilus galloprovincialis across three particle concentrations (1.5, 15, 150 mg l -1 ). Exposure to PVC for 35 days lowered mussel body condition index by 14% in relation to clay, but no difference in byssus production, respiration and survival rates emerged between the two particle types. This suggests that the effects of synthetic particles on filter feeders may emulate those of natural suspended solids, and highlights the importance of including natural particles in microplastic exposure studies., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

A combination of surface tension, surface-specific vibrational spectroscopy, and differential scanning calorimetry experiments was performed to examine the ability of lipid films to enrich interfacial organic content by attracting soluble, neutral saccharides from bulk aqueous solution. This "cooperative adsorption" hypothesis has been proposed as a possible source of the high organic fractions found in sea spray aerosols and is believed to be responsible for cryoprotection in some organisms. Experiments described in this work show that the neutral disaccharide trehalose (Tre) is drawn to lipid films composed of dipalmitoylphosphatidylcholine (DPPC), a saturated lipid that is a major component of most eukaryotic cells. The effects of Tre on DPPC monolayer structure and organization were tested with tightly packed monolayers in the two-dimensional solid phase (40 Å 2 /molecule) and more expanded monolayers in the two-dimensional liquid condensed phase (55 Å 2 /molecule). Surface tension data show that DPPC monolayer behavior remains largely unchanged until Tre bulk concentrations are sufficiently high (≥50 mM). In contrast, surface-specific vibrational sum frequency spectra show that when Tre bulk concentrations are ≥10 mM, DPPC monolayers in their liquid condensed state (55 Å 2 /molecule) became more ordered, implying relatively strong noncovalent interactions between the two species. Tre also induces changes in DPPC bilayer behavior as evidenced by a gel-to-liquid crystalline phase transition temperature that increases with increasing Tre concentration. This result suggests that Tre associates with the DPPC headgroups in very specific ways leading to partial dehydration. Together, these results support the cooperative adsorption mechanism under some circumstances, namely, that there is a minimum aqueous phase Tre concentration required to induce observable structural changes in a lipid monolayer and that these effects are most pronounced with DPPC monolayers in their liquid condensed state compared to those of a tightly packed two-dimensional solid.

Roughly a third (~30 ppm) of the carbon dioxide (CO 2 ) that entered the ocean during ice ages is attributed to biological mechanisms. A leading hypothesis for the biological drawdown of CO 2 is iron (Fe) fertilisation of the high latitudes, but modelling efforts attribute at most 10 ppm to this mechanism, leaving ~20 ppm unexplained. We show that an Fe-induced stimulation of dinitrogen (N 2 ) fixation can induce a low latitude drawdown of 7-16 ppm CO 2 . This mechanism involves a closer coupling between N 2 fixers and denitrifiers that alleviates widespread nitrate limitation. Consequently, phosphate utilisation and carbon export increase near upwelling zones, causing deoxygenation and deeper carbon injection. Furthermore, this low latitude mechanism reproduces the regional patterns of organic δ 15 N deposited in glacial sediments. The positive response of marine N 2 fixation to dusty ice age conditions, first proposed twenty years ago, therefore compliments high latitude changes to amplify CO 2 drawdown.

The isotopes of thorium (Th) and neodymium (Nd) are used as tracers in oceanography, and are key parameters in the international GEOTRACES program. The very low concentrations of Th and Nd as well as the reactive nature of Th isotopes makes the analysis of seawater samples a complex process. Analysis requires time-consuming pre-concentration from over 5 L of seawater. We describe a method to simultaneously pre-concentrate dissolved Th and Nd from acidified seawater samples using the Nobias ® PA1L chelating resin. Prior to pre-concentration, hydrofluoric acid is added to the sample to stabilise Th, ammonium acetate buffer added (0.05 M), pH adjusted to 4.75, and then finally the prepared sample is pumped through the Nobias resin at a rate of 15 ml min -1 . Up to 6 samples can be processed simultaneously. Following elution in 3 M HNO 3 , both elements are chromatographically separated and determined using Inductively Coupled Plasma Mass Spectrometry. Oxidation of the sample between all column separation steps, including after the initial Nobias resin, is important for obtaining maximum elemental recoveries. The method has >90% recovery with blank levels typically <10 pg for 232 Th and <70 pg for Nd. Accuracy is excellent, as our reported values generally agree within 1% of the GEOTRACES intercalibration standards. The long-term analysis of these materials also indicates excellent reproducibility. The pre-concentration of Th and Nd using the Nobias resin is a time saving option compared to the widely used iron co-precipitation technique. Sample handling is also reduced, decreasing the risk of sample contamination. The simplicity of our suggested pre-concentration procedure makes it possible to be applied at sea., (Copyright © 2019 Elsevier B.V. All rights reserved.)

Surface tension, surface-specific vibrational spectroscopy and differential scanning calorimetry measurements were all used to test cooperative adsorption of glucuronic acid (GU) to DPPC monolayers adsorbed to the aqueous/vapor interface. Experiments were performed using GU solutions prepared in Millipore water and in carbonate/bicarbonate solutions buffered to a pH of 9.0. The effects of GU on DPPC monolayer structure and organization were carried out with tightly packed monolayers (40 Å 2 /DPPC) and monolayers in their liquid condensed phase (55 Å 2 /molecule). Surface tension data show that GU concentrations of 50 mM lead to expanded DPPC monolayers with diminished surface tensions (or higher surface pressures) at a given DPPC coverage relative to monolayers on pure water. With unbuffered solutions, GU induces significant ordering within liquid condensed monolayers although the effects of GU on tightly packed DPPC monolayers are less pronounced. GU also induces a second, higher melting temperature in DPPC vesicles implying that GU (at sufficiently high concentrations) strengthens lipid-lipid cohesion, possibly by replacing water solvating the DPPC headgroups. Together, these observations all support a cooperative adsorption mechanism. In buffer solutions, the effects of dissolved GU on DPPC structure and organization are muted. Only at sufficiently high GU concentrations (when the solution's buffering capacity has been exceeded) do the data again show evidence of cooperative adsorption. These findings place limits on cooperative adsorption's ability to enrich interfacial organic content in alkaline environmental systems such as oceans.

We have developed a method for the determination of copper in natural waters at nanomolar levels. The use of a microplate-reader minimizes sample processing time (~25 s per sample), reagent consumption (~120 μL per sample), and sample volume (~700 μL). Copper is detected by chemiluminescence. This technique is based on the formation of a complex between copper and 1,10-phenanthroline and the subsequent emission of light during the oxidation of the complex by hydrogen peroxide. Samples are acidified to pH 1.7 and then introduced directly into a 24-well plate. Reagents are added during data acquisition via two reagent injectors. When trace metal clean protocols are employed, the reproducibility is generally less than 7% on blanks and the detection limit is 0.7 nM for seawater and 0.4 nM for freshwater. More than 100 samples per hour can be analyzed with this technique, which is simple, robust, and amenable to at-sea analysis. Seawater samples from Storm Bay in Tasmania illustrate the utility of the method for environmental science. Indeed other trace metals for which optical detection methods exist (e.g., chemiluminescence, fluorescence, and absorbance) could be adapted to the microplate-reader.

Microwave-assisted, hydrofluoric acid digestion is an increasingly common tool for the preparation of marine sediment samples for analysis by a variety of spectrometric techniques. Here we report that analysis of terrigenous-dominated sediment samples occasionally results in anomalously low values for several elements, including Al, Ba, Ca, Mg, and Sr. Measured concentrations of these elements increased with time between sample preparation and sample analysis, reaching stable values after 8-29 days. This lag is explained by the formation and subsequent dissolution of poorly soluble fluoride phases during digestion. Other elements, such as Fe, Mn, and Ti, showed little or no lag and were quickly measurable at a stable value. Full re-dissolution of the least soluble fluorides, which incorporate Al and Mg, requires up to four weeks at room temperature, and this duration can vary among sedimentary matrices. This waiting time can be reduced to 6 days (or shorter) if the samples are heated to ≈ 60°C for 24h., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The availability of iron is known to exert a controlling influence on biological productivity in surface waters over large areas of the ocean and may have been an important factor in the variation of the concentration of atmospheric carbon dioxide over glacial cycles. The effect of iron in the Southern Ocean is particularly important because of its large area and abundant nitrate, yet iron-enhanced growth of phytoplankton may be differentially expressed between waters with high silicic acid in the south and low silicic acid in the north, where diatom growth may be limited by both silicic acid and iron. Two mesoscale experiments, designed to investigate the effects of iron enrichment in regions with high and low concentrations of silicic acid, were performed in the Southern Ocean. These experiments demonstrate iron's pivotal role in controlling carbon uptake and regulating atmospheric partial pressure of carbon dioxide.