Beyond the Fe-P-redox connection: preferential regeneration of phosphorus from organic matter as a key control on Baltic Sea nutrient cycles

Patterns of regeneration and burial of phosphorus (P) in the Baltic Sea are strongly dependent on redox conditions. Redox varies spatially along water depth gradients and temporally in response to the seasonal cycle and multidecadal hydrographic variability. Alongside the well-documented link between iron oxyhydroxide dissolution and release of P from Baltic Sea sediments, we show that preferential remineralization of P with respect to carbon (C) and nitrogen (N) during degradation of organic matter plays a key role in determining the surplus of bioavailable P in the water column. Preferential remineralization of P takes place both in the water column and upper sediments and its rate is shown to be redox-dependent, increasing as reducing conditions become more severe at greater water-depth in the deep basins. Existing Redfield-based biogeochemical models of the Baltic may therefore underestimate the imbalance between N and P availability for primary production, and hence the vulnerability of the Baltic to sustained eutrophication via the fixation of atmospheric N. However, burial of organic P is also shown to increase during multidecadal intervals of expanded hypoxia, due to higher net burial rates of organic matter around the margins of the deep basins. Such intervals may be characterized by basin-scale acceleration of all fluxes within the P cycle, including productivity, regeneration and burial, sustained by the relative accessibility of the water column P pool beneath a shallow halocline

Hypoxia in the Holocene Baltic Sea : Comparing modern versus past intervals using sedimentary trace metals

Anthropogenic nutrient input has caused a rapid expansion of bottom water hypoxia in the Baltic Sea over the past century. Two earlier intervals of widespread hypoxia, coinciding with the Holocene Thermal Maximum (HTMHI; 8-4 ka before present; BP) and the Medieval Climate Anomaly (MCA(HI); similar to 1200-750 years BP), have been identified from Baltic Sea sediments. Here we present sediment records from two sites in the Baltic Sea, and compare the trace metal (As, Ba, Cd, Cu, Mo, Ni, Pb, Re, Sb, Tl, U, V, Zn) enrichments during all three hypoxic intervals. Distinct differences are observed between the intervals and the various elements, highlighting the much stronger perturbation of trace metal cycles during the modern hypoxic interval. Both Mo and U show a strong correlation with C-org and very high absolute concentrations, indicative of frequently euxinic bottom waters during hypoxic intervals. During the modern hypoxic interval (Modern(HI)) comparatively less Mo is sequestered relative to C-org than in earlier intervals. This suggests partial drawdown of the water column Mo inventory in the modern water column due to persistent euxinia and only partial replenishment of Mo through North Sea inflows. Molybdenum contents in modern sediments are likely also affected by the recent slowdown in input of Mo in association with deposition of Fe and Mn oxides. Strong enrichments of U in recent sediments confirm that the Modern(HI) is more intense than past intervals. These results suggest that U is a more reliable indicator for the intensity of bottom water deoxygenation in the Baltic Sea than Mo. Sedimentary Re enrichment commences under mildly reducing conditions, but this element is not further enriched under more reducing conditions. Enrichments of V are relatively minor for the MCA(HI) and Modern(HI), possibly due to strong reservoir effects on V in the water column, indicating that V is unreliable as an indicator for the intensity of bottom water hypoxia in this setting. Furthermore, Ba profiles are strongly influenced by post-depositional remobilization throughout the Holocene. The strong relationship between C-org and Ni, Tl and particularly Cu suggests that these trace metals can be used to reconstruct the C-org flux into the sediments. Profiles of As, Sb and Cd and especially Pb and Zn are strongly influenced by anthropogenic pollution.Peer reviewe

A key role for iron-bound phosphorus in authigenic apatite formation in North Atlantic continental platform sediments

A combination of pore water and solid phase analysis was used to determine whether authigenic carbonate fluorapatite (CFA) is currently forming in the sediment at two locations (OMEX I and II) on the North Atlantic continental platform Goban Spur (southwest of Ireland). Results of selective P extractions suggest that an early diagenetic redistribution of Fe-bound P to an authigenic P phase may be occurring at both stations. A steady-state diagenetic model describing the depth profiles of pore water HPO42− and three solid phase forms of P (organic P, Fe-bound P and authigenic P) was developed and applied to the data of station OMEX-I. The model results indicate that CFA formation can account for the observed increase of authigenic P with depth at this station. Furthermore, the results show that an intense cycling of P between Fe-bound P and pore water HPO42− at the redox interface can create conditions beneficial for CFA formation. This internal P cycle is driven by downward, bioturbational transport of mainly in-situ-formed Fe-bound P into the reduced sediment zone. Losses from the internal P cycle due to CFA formation and HPO42− diffusion are compensated for by sorption of HPO42− released from organic matter to Fe oxides in the oxidized surface sediment. Fe-bound P thus acts as an intermediate between organic P and CFA. CFA can account for between 25 and 70% of the total burial flux of reactive P at station OMEX-I and thus may act as an important sink for P in this low sedimentation, continental margin environment

Warming, euxinia and sea level rise during the Paleocene–Eocene Thermal Maximum on the Gulf Coastal Plain: implications for ocean oxygenation and nutrient cycling

The Paleocene–Eocene Thermal Maximum(PETM, ?56 Ma) was a ?200 kyr episode of globalwarming, associated with massive injections of 13C-depletedcarbon into the ocean–atmosphere system. Although climatechange during the PETM is relatively well constrained,effects on marine oxygen concentrations and nutrientcycling remain largely unclear. We identify the PETM in asediment core from the US margin of the Gulf of Mexico.Biomarker-based paleotemperature proxies (methylationof branched tetraether–cyclization of branched tetraether(MBT–CBT) and TEX86) indicate that continental air andsea surface temperatures warmed from 27–29 to ?35 ?C,although variations in the relative abundances of terrestrialand marine biomarkers may have influenced these estimates.Vegetation changes, as recorded from pollen assemblages,support this warming.The PETM is bracketed by two unconformities. It overliesPaleocene silt- and mudstones and is rich in angular(thus in situ produced; autochthonous) glauconite grains,which indicate sedimentary condensation. A drop in the relativeabundance of terrestrial organic matter and changesin the dinoflagellate cyst assemblages suggest that risingsea level shifted the deposition of terrigenous material landward.This is consistent with previous findings of eustatic sealevel rise during the PETM. Regionally, the attribution of theglauconite-rich unit to the PETM implicates the dating of aprimate fossil, argued to represent the oldest North Americanspecimen on record.The biomarker isorenieratene within the PETM indicatesthat euxinic photic zone conditions developed, likely seasonally,along the Gulf Coastal Plain. A global data compilationindicates that O2 concentrations dropped in allocean basins in response to warming, hydrological change,and carbon cycle feedbacks. This culminated in (seasonal)anoxia along many continental margins, analogous to moderntrends. Seafloor deoxygenation and widespread (seasonal)anoxia likely caused phosphorus regeneration fromsuboxic and anoxic sediments.We argue that this fueled shelfeutrophication, as widely recorded from microfossil studies,increasing organic carbon burial along many continentalPublished by Copernicus Publications on behalf of the European Geosciences Union.Warming, euxinia and sea level rise during the PETMmargins as a negative feedback to carbon input and globalwarming. If properly quantified with future work, the PETMoffers the opportunity to assess the biogeochemical effects ofenhanced phosphorus regeneration, as well as the timescaleson which this feedback operates in view of modern and futureocean deoxygenation

Iron-Phosphorus Feedbacks Drive Multidecadal Oscillations in Baltic Sea Hypoxia

Hypoxia has occurred intermittently in the Baltic Sea since the establishment of brackish-water conditions at similar to 8,000 years B.P., principally as recurrent hypoxic events during the Holocene Thermal Maximum (HTM) and the Medieval Climate Anomaly (MCA). Sedimentary phosphorus release has been implicated as a key driver of these events, but previous paleoenvironmental reconstructions have lacked the sampling resolution to investigate feedbacks in past iron-phosphorus cycling on short timescales. Here we employ Laser Ablation (LA)-ICP-MS scanning of sediment cores to generate ultra-high resolution geochemical records of past hypoxic events. We show that in-phase multidecadal oscillations in hypoxia intensity and iron-phosphorus cycling occurred throughout these events. Using a box model, we demonstrate that such oscillations were likely driven by instabilities in the dynamics of iron-phosphorus cycling under preindustrial phosphorus loads, and modulated by external climate forcing. Oscillatory behavior could complicate the recovery from hypoxia during future trajectories of external loading reductions.Peer reviewe

Recovery from multi‐millennial natural coastal hypoxia in the Stockholm Archipelago, Baltic Sea, terminated by modern human activity

Enhanced nutrient input and warming have led to the development of low oxygen (hypoxia) in coastal waters globally. For many coastal areas, insight into redox conditions prior to human impact is lacking. Here, we reconstructed bottom water redox conditions and sea surface temperatures (SSTs) for the coastal Stockholm Archipelago over the past 3000 yr. Elevated sedimentary concentrations of molybdenum indicate (seasonal) hypoxia between 1000b.c.e.and 1500c.e. Biomarker-based (TEX86) SST reconstructions indicate that the recovery from hypoxia after 1500c.e.coincided with a period of significant cooling (similar to 2 degrees C), while human activity in the study area, deduced from trends in sedimentary lead and existing paleobotanical and archeological records, had significantly increased. A strong increase in sedimentary lead and zinc, related to more intense human activity in the 18(th)and 19(th)century, and the onset of modern warming precede the return of hypoxia in the Stockholm Archipelago. We conclude that climatic cooling played an important role in the recovery from natural hypoxia after 1500c.e., but that eutrophication and warming, related to modern human activity, led to the return of hypoxia in the 20(th)century. Our findings imply that ongoing global warming may exacerbate hypoxia in the coastal zone of the Baltic Sea

Understanding Environmental Changes in Temperate Coastal Seas : Linking Models of Benthic Fauna to Carbon and Nutrient Fluxes

Coastal seas are highly productive systems, providing an array of ecosystem services to humankind, such as processing of nutrient effluents from land and climate regulation. However, coastal ecosystems are threatened by human-induced pressures such as climate change and eutrophication. In the coastal zone, the fluxes and transformations of nutrients and carbon sustaining coastal ecosystem functions and services are strongly regulated by benthic biological and chemical processes. Thus, to understand and quantify how coastal ecosystems respond to environmental change, mechanistic modeling of benthic biogeochemical processes is required. Here, we discuss the present model capabilities to quantitatively describe how benthic fauna drives nutrient and carbon processing in the coastal zone. There are a multitude of modeling approaches of different complexity, but a thorough mechanistic description of benthic-pelagic processes is still hampered by a fundamental lack of scientific understanding of the diverse interactions between the physical, chemical and biological processes that drive biogeochemical fluxes in the coastal zone. Especially shallow systems with long water residence times are sensitive to the activities of benthic organisms. Hence, including and improving the description of benthic biomass and metabolism in sediment diagenetic as well as ecosystem models for such systems is essential to increase our understanding of their response to environmental changes and the role of coastal sediments in nutrient and carbon cycling. Major challenges and research priorities are (1) to couple the dynamics of zoobenthic biomass and metabolism to sediment reactive-transport in models, (2) to test and validate model formulations against real-world data to better incorporate the context-dependency of processes in heterogeneous coastal areas in models and (3) to capture the role of stochastic events.Peer reviewe

Associations between the LEP -2548G/A Promoter and Baseline Weight and between LEPR Gln223Arg and Lys656Asn Variants and Change in BMI z Scores in Arab Children and Adolescents Treated with Risperidone

Data on baseline (antipsychotic-naïve) age, weight, and height and change in these over three subsequent follow up time points up to 313.6 days (CI 303.5-323.7), were collected from 181 risperidone-treated children and adolescents (mean age 12.58 years, SD 4.99, range 2.17-17.7) attending a pediatric neurology clinic in Saudi Arabia. Owing to differences in genotypic distributions in subsamples, results are reported from the white Arabs (N=144). Age and gender-normed BMI-standardised z scores (BMI z) were calculated (lmsgrowth program). Linear regression was performed for baseline weight and BMI z, while change in BMI z was assessed using random effects ordered logistic regression. The following SNPs were analyzed: rs7799039 in the LEP promoter, rs1805094 (previously rs8179183), rs1137100 and rs1137101 in the LEPR, and rs1414334 in HTR2C. We found a nominally significant association between rs7799309 and baseline weight, adjusting for height, age, gender and diagnosis (A/G, P=0.035, β=-3.62, compared to G/G). rs1137101 (G/G, P=0.018, OR=4.13 compared to A/A) and rs1805094 C-allele carriers (P=0.019, OR=0.51) showed nominally significant associations with change in BMI z categories. Our data support and replicate previous relevant associations for these variants including with weight gain on risperidone, whilst being the first to report such associations in those of Arab ethnicity