Regression-based distribution mapping for bias correction of climate model outputs using linear quantile regression

Stochastic Environmental Research and Risk Assessment - Impact models are a major source of information for quantifying the consequences of future climate change for humans and the environment. To...     

Biological controls on dissolution of diatom frustules during their descent to the deep ocean: Lessons learned from controlled laboratory experiments

The majority of opal produced by diatoms dissolves during their sedimentation to the seafloor, but spatial and temporal variability of dissolution rates are large. Controlled laboratory experiments using live phytoplankton or phyto-detritus may help identify the different processes, including those that are biologically mediated or physico-chemically driven, that impact the dissolution of frustules and the aforementioned variability. Results of eight bSiO₂ dissolution experiments, seven of which were conducted at low temperatures (<6 °C) are presented within the context of earlier similar studies, and different phases of dissolution dynamics characterized. TEP concentration, aggregation and the physiological status of the diatoms determined the period during which diatoms may maintain the protective membrane that surrounds their frustule and effectively reduces or completely inhibits (lag period) dissolution for some time. Once diatoms loose the capability to maintain their protective membrane, bacterial activity compromises it. Physico-chemical dissolution, which depends on frustule structure and abiotic environmental conditions, begins once the protective membrane is damaged. The ability of diatoms to maintain their membrane, the bacterial composition and activity governing its degradation, and the physico-chemical dissolution dynamics of exposed frustules are all impacted by temperature. In our experiments instantaneous dissolution rates were not dependant on bSiO₂ concentration at low temperatures, although such a relationship was observed under otherwise identical conditions at 15 °C, implying that biotic factors rather than physico-chemical processes initially dominated dissolution at polar temperatures. Since inhibition of bSiO₂ dissolution at low temperatures was inhibited to a greater extent than organic matter degradation, we postulate that it was not reduced bacterial activity but the enhanced ability of diatoms to maintain their membrane and thus withstand microbial attack that caused the low initial dissolution rates at <6 °C. In situ, interactions between the different biotic and abiotic processes impacting dissolution combined with differences in sinking velocity of diatom aggregates and grazing effects could easily explain high spatial and temporal variability in the accumulation of diatoms on the seafloor. Simple calculations based on our experimental results suggest that Fragilariopsis kerguelensis, for example, would be appreciably more likely to reach the seafloor than Chaetoceros debilis if both grow at low growth rates, e.g. under growth limiting conditions. However, dissolution behavior of Chaetoceros debilis during sedimentation may differ under conditions where this species forms large blooms.     

Organic carbon to Th ratios of marine organic matter

Uncertainties in the determinations of particulate organic carbon flux from measurements of the disequilibrium between ²³⁴Th and its mother isotope uranium depend largely on the determination of the organic carbon to ²³⁴thorium (OC : ²³⁴Th) ratio. The variability of the OC : ²³⁴Th ratio in different size fractions of suspended matter, ranging from the truly dissolved (< 3 or 10 kDa) fraction to several millimeter sized marine snow, as well as from sediment trap material was assessed during an eight-day cruise off the coast of California in Spring 1997. The affinity of polysaccharide particles called TEP (transparent exopolymer particles) and inorganic clays to ²³⁴Th was investigated through correlations. The observed decrease in the OC : ²³⁴Th ratio with size, within the truly dissolved to small particle size range, is consistent with concepts of irreversible colloidal aggregation of non-porous nano-aggregates. No consistent trend in the OC : ²³⁴Th ratio was observed for particles between 1 or 10 to 6000 μm. Origin and fate of marine particles belonging to this size range are diverse and interactions with ²³⁴Th too complex to expect a consistent relationship between OC : ²³⁴Th ratio and size, if all categories of particles are included. The relationship between OC and ²³⁴Th was significant when data from the truly dissolved fraction were excluded. However, variability was very large, implying that OC flux calculations using different collection methods (e.g. sediment trap, Niskin bottles or pumps) would differ significantly. Therefore a large uncertainty in OC flux calculations based on the ²³⁴Th method exist due to individual decisions as to which types or size classes of particles best represent sinking material in a specific area. Preferential binding of ²³⁴Th to specific substance classes could explain the high variability in the relationship between OC and ²³⁴Th. At 15 m, in the absence of lithogenic material, the OC : ²³⁴Th ratio was a function of the fraction of TEP or TEP-precursors in OC, confirming that acidic polysaccharides have a high affinity for ²³⁴Th and that TEP carry a ligand for ²³⁴Th. Preferential binding to TEP might change distribution patterns of ²³⁴Th considerably, as TEP may sink when included in large aggregates, or remain suspended or even ascend when existing as individual particles or microaggregates. In the presence of lithogenic matter, at depths below 30 m, the ratio between ²³⁴Th and OC was linearly related to the ratio between alumino silicates and C. The affinity of inorganic substances to ²³⁴Th is known to be relatively low, suggesting that a coating of acidic polysaccharides was responsible for the apparently high affinity between ²³⁴Th and lithogenic material. Overall, OC : ²³⁴Th ratios of all material collected during this investigation can best be explained by differential binding of ²³⁴Th to both TEP and TEP-precursors, as well as to lithogenic minerals, which were very abundant in an intermediate nepheloid layer between 50 and 90 m.     

Thorium speciation in seawater

Since the 1960s, thorium isotopes occupy a special place in the oceanographer's toolbox as tracers for determining rates and mechanisms of oceanic scavenging, particle dynamics, and carbon fluxes. Due to their unique and constant production rates from soluble parent nuclides of uranium and radium, their disequilibrium can be used to calculate rates and time scales of sinking particles. In addition, by ratio-ing particulate ²³⁴Th (as well, in principle, other Th-nuclides) to carbon (and other elements), and linking this ratio to the parent–daughter disequilibrium in the water column, it is possible to calculate fluxes of carbon and other elements. Most of these applications are possible with little knowledge of the dissolved chemical properties of thorium, other than its oxidation state (IV) and tendency to strongly sorb to surfaces, i.e., its “particle- or surface-activity”. However, the use of any tracer is hindered by a lack of knowledge of its chemical properties. Recent observations in the variability of carbon to ²³⁴Th ratios in different particle types, as well as of associations of Th(IV) with various marine organic biomolecules has led to the need for a review of current knowledge and what future endeavors should be taken to understand the marine chemistry of thorium.     

Neutral aldoses as source indicators for marine snow

The chemical characteristics of aggregating material in the marine environment are largely unknown. We investigated neutral aldose (NA) abundance and composition in aggregation of marine snow and other organic matter (OM) size fractions in the field. Four sample sets were fractionated using membrane filtration and ultrafiltration into the following size fractions: particulate material, high-molecular-weight (HMW) material, and low-molecular-weight (LMW) material. We also collected three sample sets of marine-snow aggregates. Each sample set contained small, medium, and large aggregate size fractions and each size fraction consisted of 25–50 aggregates. For 7 marine-snow samples and for each water-sample size fraction, we determined monomeric and polymeric NA concentration, NA yield (amount of NA-C normalized to organic carbon), and composition; total organic carbon (TOC) concentration; transparent exopolymer particles (TEP) concentration, and TEP propensity (TEP concentration after inducing TEP formation in filtered samples). This is the first study to include compound-specific NA determinations on these four marine OM size fractions.The mass balances of organic carbon and NA indicated that there were no serious contamination or loss problems. Concentrations, yields, and NA mol fractions in water samples were similar to results from other studies. Glucose and galactose had the highest relative abundance in all size fractions. The NA yield increased with increasing molecular weight or particle size for all fractions except marine snow. The NA yield increased in the order: LMW< marine snow< HMW< particles. Marine snow had a higher average NA yield than the LMW fraction, but lower than particle and HMW-fractions. This indicates that OM in marine snow could have been diagenetically derived from particulate and HMW-fractions, that is, marine snow may include material from the particulate and the colloidal phase.TEP concentration or TEP propensity was positively correlated with concentrations of all individual NAs as well as the sum NA concentrations, indicating that TEP contains neutral sugars in addition to the acidic polysaccharides stained in the determination of TEP concentrations.Despite the relatively low NA yield in marine snow, marine snow was enriched in NA when compared with seawater, with enrichment factors of 34–225 (average 125). By combining data from this study with data from other studies, we estimate that < 10% of carbohydrates in marine snow comprise NAs.There was no clear correlation between marine-snow aggregate size and NA yield, that is, there appears to be no general age difference between small and large marine-snow aggregates. NA composition was similar among different marine-snow size fracions collected during the same day, indicating that aggregation/disaggregation reactions resulted in homogenizing NA composition in marine-snow aggregates of all sizes. The NA composition of marine snow was different from that of other OM size fractions, indicating either that bacterial degradation has modified the composition of marine snow to a larger extent than other OM size fractions or that marine snow is formed through the aggregation of selected subcomponents of OM.     

An assessment of particulate organic carbon to thorium-234 ratios in the ocean and their impact on the application of Th as a POC flux proxy

Thorium-234 is increasingly used as a tracer of ocean particle flux, primarily as a means to estimate particulate organic carbon export from the surface ocean. This requires determination of both the ²³⁴Th activity distribution (in order to calculate ²³⁴Th fluxes) and an estimate of the C / ²³⁴Th ratio on sinking particles, to empirically derive C fluxes. In reviewing C / ²³⁴Th variability, results obtained using a single sampling method show the most predictable behavior. For example, in most studies that employ in situ pumps to collect size fractionated particles, C / ²³⁴Th either increases or is relatively invariant with increasing particle size (size classes > 1 to 100s μm). Observations also suggest that C / ²³⁴Th decreases with depth and can vary significantly between regions (highest in blooms of large diatoms and highly productive coastal settings). Comparisons of C fluxes derived from ²³⁴Th show good agreement with independent estimates of C flux, including mass balances of C and nutrients over appropriate space and time scales (within factors of 2–3). We recommend sampling for C / ²³⁴Th from a standard depth of 100 m, or at least one depth below the mixed layer using either large volume size fractionated filtration to capture the rarer large particles, or a sediment trap or other device to collect sinking particles. We also recommend collection of multiple ²³⁴Th profiles and C / ²³⁴Th samples during the course of longer observation periods to better sample temporal variations in both ²³⁴Th flux and the characteristic of sinking particles. We are encouraged by new technologies which are optimized to more reliably sample truly settling particles, and expect the utility of this tracer to increase, not just for upper ocean C fluxes but for other elements and processes deeper in the water column.