Colloidal rare earth elements in a boreal river: Changing sources and distributions during the spring flood

Variations in the physico-chemical speciation of the rare earth elements (REE) have been investigated in a subarctic boreal river during an intense spring flood event using prefiltered (<100 μm) samples, cross-flow (ultra)filtration (CFF), flow field-flow fractionation (FlFFF), and diffusive gradients in thin films (DGT). This combination of techniques has provided new information regarding the release and transport of the REE in river water. The colloidal material can be described in terms of two fractions dominated by carbon and iron, respectively. These two fractions, termed colloidal carrier phases, showed significant temporal changes in concentration and size distribution. Before the spring flood, colloidal carbon concentrations were low, the colloids being dominated by relatively large iron colloids. Colloidal concentrations increased sharply during the spring flood, with smaller carbon colloids dominating. Following the spring flood, colloidal concentrations decreased again, smaller carbon colloids still dominating. The REE are transported mainly in the particulate and colloidal phases. Before the spring flood, the REE composition of all measured fractions was similar to local till. During the spring flood, the REE concentrations in the colloidal and particulate fractions increased. The increase was most marked for the lighter REE, which therefore showed a strong enrichment when normalized to local till. Following the spring flood, the REE concentrations decreased again and reverted to a distribution similar to local till. These changes in the concentration and distributions of carbon iron and REE are interpreted in terms of changing hydrological flow paths in soil and bedrock which occur during the spring flood.     

2d-Spectroscopy with the Image Scanner of the Gregory-Coudé-Telescope on Tenerife

In summer 1995 a new system for spectropolarimetry in two spatial dimensions was installed and tested at the Gregory-Coudé-Telescope (GCT) at the Observatorio del Teide (Izaña, Tenerife). The system consists of a scanning device, which is free of instrumental polarization, and a fast CCD camera. During scanning the solar image is moved across the entrance slit of the spectrograph and at a selected number of positions spectra are taken. Fast spectropolarimetry is the main goal of the scientific applications.     

Association of calcium with colloidal particles and speciation of calcium in the Kalix and Amazon rivers

A considerable amount of colloidally bound Ca has been detected in water samples from Amazonian rivers and the Kalix River, a sub-arctic boreal river. Fractionation experiments using several analytical techniques and processing tools were conducted in order to elucidate the matter. Results show that on average 84% of the total Ca concentration is present as free Ca. Particulate, colloidal and complexed Ca constitute the remaining 16%, of which the colloidal fraction is significant. Ultrafiltration experiments show that the colloidal fraction in the sampled Amazonian rivers and the Kalix River range between 1% and 25%.In both the Amazonian and the Kalix rivers the technique of cross-flow ultrafiltration was used to isolate particles and colloids. The difference in concentration measured with ICP-AES and a Ca ion-selective electrode in identical samples was used to define the free Ca concentration and thus indirectly the magnitude of the particulate, colloidal and complexed fractions. Results from the Kalix and Amazonian rivers are in excellent agreement. Furthermore, the results show that the colloidal concentrations of Ca can be greatly overestimated (up to 227%) when conventional analysis and calculation of ultrafiltration data is used due to retention of free Ca ions during the ultrafiltration process. Calculation methods for colloidal matter are presented in this work, using complementary data from ISE analysis.In the Kalix River temporal changes in the fractionation of Ca were studied before, during and after a spring-flood event. Changes in the size distribution of colloidally associated Ca was studied using FlFFF (Flow Field-Flow Fractionation) coupled on-line to a HR ICP-MS. The FlFFF-HR ICP-MS fractograms clearly show the colloidal component of Ca, supporting the ultrafiltration findings. During winter conditions the size distribution of colloidally associated Ca has a concentration maximum at ∼5 to 10 nm in diameter, shifting to smaller sizes (<5 nm) during and after the spring flood. This shift in size distribution follows a change in the river during this period from ironoxyhydroxy colloids being the most important colloidal carrier phase to humic substances during and after the spring flood.WHAM and NICA-Donnan models were used to calculate the amount of colloidally bound Ca. The results similar for both models, show that on average 16% of the Ca may be associated to a colloidal phase, which is in broad agreement with the measurements.     

Temporal variations of colloidal carrier phases and associated trace elements in a boreal river

Elemental size distributions, from truly dissolved through colloidal to particulate, have been studied in a subarctic boreal river. The measurements, carried out during 2002, ranged from winter to summer conditions, including an intense spring flood event. Results are reported for a total of 42 elements. Size distributions were characterised using a combination of cross-flow (ultra)filtration (CFF), flow field-flow fractionation (FlFFF), and diffusive gradients in thin-films (DGT). The three techniques showed similar trends, but quantitative comparisons reveal some important differences that warrant further investigation.Previous work has identified two colloidal carrier phases in fresh waters, dominated by iron and carbon, respectively. The majority of the elements studied are associated with one or both of these colloidal carrier phases. The exceptions are the alkali metals and several anions that are only very weakly associated with colloidal material, and which therefore occur mainly as truly dissolved material (<1 kDa in molecular weight). We discuss the likely origin for the two colloidal carrier phases and consider how associated trace elements fit into the geochemical framework. The relative affinities of the elements for iron and carbon colloidal carrier phases are related to their chemistries, and are compared with earlier data from the Delsjö Creek in southern Sweden.Elemental colloidal concentrations show strong seasonal variations related to changes in the colloidal carrier phase(s) with which they associate. In particular, many elements show a strong spring maximum in colloidal concentrations associated with the strong maximum in colloidal carbon concentration during the spring flood.     

High resolution observations of small-scale magnetic elements and interpretation

This contribution deals with the properties of small-scale magnetic elements in plages. Spectro-polarimetric observations, obtained with the highest possible spatial resolution with the German solar telescopes at the Observatorio del Teide on Tenerife, were analysed. We conclude from the spread of line parameters measured in the Stokes I and V profiles of Fe I and Fe II lines that a wide range of magnetic properties is realised in the solar atmosphere. The flow velocities in small-scale magnetic flux tubes, deduced from the zero-crossing of the V profiles at high spatial resolution, show a fluctuation of v _Doppler = 580 m s^-1. This is substantially smaller than the turbulent broadening velocities of v _Doppler = 2 – 3 km s^–1 commonly derived by fitting V profiles from flux tube models to low spatial resolution data, e.g. from a Fourier Transform Spectrometer. Attempts to explain the high resolution I and V profiles by models of hydrostatic flux tubes are discussed. It appears impossible to accomplish agreement between the modeled and observed radiation of lines with strong and weak magnetic sensitivity at the same time. We suggest a scenario in which small-scale magnetic elements possess substructure and are dynamic, with gas flows and magnetic field strengths varying in space and time.     

Pacific variability reconciles observed and modelled global mean temperature increase since 1950

Global mean temperature change simulated by climate models deviates from the observed temperature increase during decadal-scale periods in the past. In particular, warming during the ‘global warming hiatus’ in the early twenty-first century appears overestimated in CMIP5 and CMIP6 multi-model means. We examine the role of equatorial Pacific variability in these divergences since 1950 by comparing 18 studies that quantify the Pacific contribution to the ‘hiatus’ and earlier periods and by investigating the reasons for differing results. During the ‘global warming hiatus’ from 1992 to 2012, the estimated contributions differ by a factor of five, with multiple linear regression approaches generally indicating a smaller contribution of Pacific variability to global temperature than climate model experiments where the simulated tropical Pacific sea surface temperature (SST) or wind stress anomalies are nudged towards observations. These so-called pacemaker experiments suggest that the ‘hiatus’ is fully explained and possibly over-explained by Pacific variability. Most of the spread across the studies can be attributed to two factors: neglecting the forced signal in tropical Pacific SST, which is often the case in multiple regression studies but not in pacemaker experiments, underestimates the Pacific contribution to global temperature change by a factor of two during the ‘hiatus’; the sensitivity with which the global temperature responds to Pacific variability varies by a factor of two between models on a decadal time scale, questioning the robustness of single model pacemaker experiments. Once we have accounted for these factors, the CMIP5 mean warming adjusted for Pacific variability reproduces the observed annual global mean temperature closely, with a correlation coefficient of 0.985 from 1950 to 2018. The CMIP6 ensemble performs less favourably but improves if the models with the highest transient climate response are omitted from the ensemble mean.