Marine diatom uptake of iron bound with natural colloids of different origins

Natural colloids are abundant in seawater and are an intermediary in the fate, transport and bioavailability of many trace elements. Knowledge of the pathways and mechanisms of the biological uptake of colloidal Fe and other Fe species is of paramount importance in understanding Fe limitation on marine phytoplankton and thus carbon sequestration in the ocean. Whether the natural colloids serve as a source for the biological Fe requirements of marine phytoplankton, or just as a sink for particle-reactive metals in the oceans remains largely unknown. This study examined the bioavailability of Fe bound with colloids from different regions to a coastal diatom (Thalassiosira pseudonana). Natural colloids were isolated by cross-flow ultrafiltration and radiolabeled with ⁵⁹Fe before being exposed to phytoplankton. Control experiments were conducted to ensure that ⁵⁹Fe radiolabeled onto the colloids remained mostly in the colloidal phase. Both the natural oceanic and coastal colloidal organic matter complexed Fe (1 nm–0.2 μm) can be biologically available to the marine diatom even though its uptake was lower than the low molecular weight counterparts. By comparing the measured Fe internalization fluxes and the calculated maximum diffusive uptake fluxes, it is evident that ligand exchange kinetics on the cell surface may control the internalization of macromolecular Fe. The calculated concentration factors under dark and light conditions were generally comparable. Colloidal Fe, as an important intermediary phase, can be actively involved in the planktonic food web transfer through biological uptake and regeneration processes. The bioavailable fraction of Fe may be substantially underestimated by only considering the truly dissolved Fe or overestimated when using the external fluxes, such as aerosol Fe, as the bioavailable fraction.     

Climate change and sustainable development: towards dialogue

The consequences of climate change and sustainable development remaining as separate discourses are explored, both in general and in the Canadian context. One of these consequences is the difference in emission and economic development scenarios generated by the two groups. A second is that strategies to reduce greenhouse gas emissions are designed and assessed in a narrow technical context, divorced from the economic and social forces that underlie them. We identify the need for climate change and sustainable development to be represented in a more explicit manner in each other's research agendas, and for integrated assessment of climate change to incorporate alternative methodologies that complement global scale integrated assessment models. These methodologies should include greater involvement of stakeholders as partners with researchers in a shared learning experience.     

Characterization of natural colloids from a river and spring in a karstic basin

 Colloids are known to transport contaminants over long distances in natural media. Despite this potentially harmful effect, very few studies have been undertaken in subsurface aquifers. This paper presents the first results of a study of natural colloids and particles in a karstic aquifer. The site was chosen for its coverage by clay layers and peat which deliver various and numerous particle types in water. The methodological part describes three methods used for size determination and sample fractionation of surface water and spring water. These methods have been adapted for the treatment of multiple samples due to the rapid discharge variation typical of karstic aquifers. The analysis of many particle size distributions (PSD) shows that they can be described by a Pareto law. The variation of the slope of the PSD at the spring is mainly dependent on discharge. This behavior is interpreted as a washing of the karstic drains during the first phase of high flow events. Fractionation of the samples allowed application of various characterization techniques to particle size classes. X-ray diffraction (XRD) patterns showed that most of the mineral particles originated from Quaternary deposits and limestones. However the use of scanning electron micrsocopy with energy-dispersive spectrometer (SEM-EDS) detailed the composition of individual particles and revealed particles not found by XRD. These techniques also showed the high complexity of the natural particles and the important place of coprecipitation in their formation. Consequences on the fluxes of particulate matter and its potential role as a carrier of contaminants are discussed. Received: 28 October 1996 · Accepted: 7 July 1997     

Characterization of colloidal and particulate matter transported by the magela creek system,Northern Australia

The composition and amount of colloidal and suspended participate matter transported during a small flood event in Magela Creek in tropical northern Australia was investigated. The flood studied constituted approximately 3 % of the total annual flow, most (90%) of which occurred between mid-January and mid-February of the study year. Three fractions were separated from water samples using a sequential method involving a continuous flow centrifuge to separate suspended particulate matter (SPM; nominally > 1 μm) followed by hollow fibre filtration, first using a 0.1 μm filter to separate course colloidal matter (CCM; nominal size 1–0.1 μm) and then a 0–015 μm filter to separate fine colloidal matter (FCM; nominal size 0.1–0.015 μm). The SPM was predominantly inorganic (organic matter 21 %), whereas the colloidal fractions were dominantly organic matter (CCM 60%; FCM 83%). Analysis of individual particles using electron microprobe and automated image analysis indicated that the mineral fractions in both the SPM and CCM were dominated by iron-enriched aluminosilicates (including kaolinite) (72–82%) and quartz (9–10%), indicative of a highly weathered and extensively laterized catchment. Surprisingly there was very little difference in the composition of the SPM or CCM fractions during the flood event studied, which may indicate either that sediment availability was restricted following the major run-off events in January and February, or that all the sediment sources within the catchment are geochemically similar. Approximately the same amounts of particulate (20 tonne), colloidal (21 tonne) and dissolved material (17 tonne) were transported during the 25 hour period of the main flood peak; over 90% of the colloidal matter was 0.1–1.0 μm in size. These data suggest that previous estimates of the amounts of particulate (and colloidal) matter transported by Magela Creek, which were based on suspended solids measurements, may have underestimated the particulate matter load by as much as 50%. It is possible that the relatively high proportion of colloidal matter is unique to Magela Creek because coagulation and aggregation of colloidal matter to particulate matter is slow due to the very low concentations of calcium and magnesium in these waters. However, if the result is more widespread, there are important implications for the global estimates of fluvially transported particulate and dissolved materials as many of the previous studies may have underestimated the particulate load and overestimated the dissolved load.     

Two-dimensional modeling of contaminant transport in porous media in the presence of colloids

It has long been known that colloids can facilitate the transport of contaminants in groundwater systems by reducing the effective retardation factor. A significant effort has been devoted to study colloid-facilitated contaminant transport during the past decade. Many of the previous studies were restricted to one-dimensional analyses and comparisons with finite-column experiments. In this work, a two-dimensional numerical model is developed and used to study the different interactions between colloids, contaminants, and porous media under homogeneous conditions. The numerical formulation of the model is based on discretizing mass balance equations and reaction equations using finite differences having a third-order, total variance-diminishing scheme for the advection terms. This scheme significantly reduces numerical dispersion and leads to greater accuracy compared to the standard central-differencing scheme. The model is tested against analytical solutions under simplified conditions as well as against experimental data, and the results are favorable. The model is used to investigate the impact of the various reaction rates and parameter values on the movement of contaminant plumes in two dimensions. The model is also used to investigate the hypothesis that colloids may increase the effective retardation factor of contaminant plumes. The analysis shows that assuming kinetic mass exchange between contaminant and colloids with constant reaction rate coefficients that are not related to the concentrations may lead to inaccurate results. These inaccurate results are exemplified in the finding that under the kinetic assumption the ratio of the initial concentration of colloids to the initial concentration of contaminant does not affect the amount of facilitation or retardation that occurs in the system. It is also found that colloids can increase the effective retardation factor for the contaminant under certain combinations of reaction rates and distribution coefficients. A quantitative empirical expression to identify whether colloids retard or facilitate the contaminant movement is presented.     

Spatial moments for colloid-enhanced radionuclide transport in heterogeneous aquifers

We consider colloid facilitated radionuclide transport by steady groundwater flow in a heterogeneous porous formation. Radionuclide binding on colloids and soil-matrix is assumed to be kinetically/equilibrium controlled. All reactive parameters are regarded as uniform, whereas the hydraulic log-conductivity is modelled as a stationary random space function (RSF). Colloid-enhanced radionuclide transport is studied by means of spatial moments pertaining to both the dissolved and colloid-bounded concentration. The general expressions of spatial moments for a colloid-bounded plume are presented for the first time, and are discussed in order to show the combined impact of sorption processes as well as aquifer heterogeneity upon the plume migration. For the general case, spatial moments are defined by the aid of two characteristic reaction functions which cannot be expressed analytically. By adopting the approximation for the longitudinal fluid trajectory covariance valid for a flow parallel to the formation bedding suggested by Dagan and Cvetkovic [Dagan G, Cvetkovic V. Spatial Moments of Kinetically Sorbing Plume in a Heterogeneous Aquifers. Water Resour Res 1993;29:4053], we obtain closed form solutions.     

Crystal chemistry of suspended matter in a tropical hydrosystem, Nyong basin (Cameroon, Africa)

Suspended matter (SM) from the Nyong basin (Cameroon, Africa), a tropical watershed, was collected by tangential flow ultrafiltration to separate particulate (>0.45 μm) and colloidal (<0.45 μm; >20 kDa) fractions. In this basin, two distinctive systems in a selected small catchment (Nsimi–Zoétélé) of the Nyong river basin have been considered: (i) colourless water (groundwater and spring) with a low suspended load (<3 mg/l) and a low total organic carbon content (TOC<1 mg/l) and (ii) coloured water (Mengong brook and Nyong river), which is organic rich (TOC>10 mg/l) and contains higher amounts of SM (10–20 mg/l) than the colourless water. Freeze-dried samples of SM have been analysed by X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), electron paramagnetic resonance spectroscopy (EPR), and visible diffuse reflectance spectroscopy (DRS).

Colourless water mainly contains mineral phases, such as poorly ordered kaolinite, plus quartz and goethite in the particulate fraction, and euhedral kaolinite plus amorphous iron oxyhydroxides in the colloidal fraction. In contrast, the SM in coloured water is mainly organic in nature. The mineral phases in the particulate fraction are similar to those from clear water, but with additional phytoliths and diatom frustules composed of biogenic opal. In the colloidal fraction, complexation of Fe³⁺ and Mn²⁺ with organic matter is evidenced by EPR, together with significant occurrence of Fe oxyhydroxides associated with organic matter.

The sites of Al, Si, Fe, Mn in colloidal fractions derived from spectroscopic analyses are discussed with reference to chemical analyses performed by inductively coupled plasma mass spectrometry. Most of the observed solid phases or species correspond to those expected from published thermodynamic calculations for the same hydrosystem, except the colloidal iron oxyhydroxides in the coloured water. The presence of such iron phases is emphasised since they are expected to have large sorption capacities for numerous trace elements.

The crystal chemistry of SM is used to discuss the origin of the mineral particles transported from the soil to the main rivers in terms of mechanical and chemical erosion processes.