Colloidal Fraction Research Articles

Mechanisms of thixotropy in cement suspensions considering influences from shear history and hydration

AbstractThe rheological properties of fresh concrete are a direct function of the interaction behaviour of the granular inventory of the concrete (i.e., gravel, sand and cement) and especially of the colloidal fractions of cement. Under low shear stresses, agglomeration of colloidal particles is observed, while at high shear stresses, dispersion of these agglomerates occurs. Besides the agglomeration state, the formation of shear banding, zones with concentrated shear flow, is another controlling mechanism of the flow behaviour of cement suspensions. Rheological creep tests in this study are focused on investigating the influence of shear history and hydration process on thixotropy of cement suspension. In this paper, the meaning of the word thixotropy is slightly extended to additionally encompass rheological aging and hydration effects. Selected samples were analyzed by coupling a rheometer to synchrotron X‐ray tomography to gain insight into the shear‐induced microstructural changes during shear start‐up tests. The observations show heterogeneities in the velocity profile in the shear gap and the development of shear banding.

Water-dispersible colloids facilitate the release of potentially toxic elements from contaminated soil under simulated long-term acid rain

The release behaviors of potentially toxic elements (PTEs) associated with water-dispersible colloids (WDCs) in contaminated soils are of considerable public concern. However, little information is available on the size distribution and elemental composition of WDCs and their effects on the release of PTEs in contaminated soils under long-term acid rain. Here, a quantitative accelerated aging leaching test was conducted to evaluate the long-term release risks of PTEs from four contaminated agricultural soil types exposed to acid rain. Asymmetric flow field-flow fractionation (AF4), scanning transmission electron microscopy-energy dispersive spectroscopy (STEM-EDS) and ultrafiltration were used to clarify the size distribution and elemental composition of WDCs containing PTEs. Solution dynamics of successive leaching indicate high release potential for As, Cd, and Pb depending on soil properties under long-term (∼65 years) acid rain. Both ultrafiltration and AF4 analysis show that As in leachate was mainly in the “truly dissolved” fraction, while Pb, Cu, Cd and Fe were predominantly in the colloidal fraction and their percentages increased with increasing extraction time by acid rain. AF4-UV-ICP-MS and STEM-EDS reveal that nanoparticles at 1–7 nm most likely composed of organic matter (OM)-Fe/Al(/Si) oxides composite were the main carriers of Pb, Cu, As and Cd. Lead was also verified in Fe-oxide colloids at 34–450 nm in the first extracts but disappeared in the tenth extracts. This indicates that WDC-bearing PTEs become smaller as leaching proceeds. The study indicates the quantitative description and size-resolved understanding of WDC- and nanoparticle-bound PTEs in leachates of contaminated soils subjected to long-term acid rain.

Copper retention influenced by an invasive and a native plant in riparian soil

Riparian soils are exposed to diverse anthropogenic stressors via aquatic pathways. Our study focuses on the impact of the invasive plant Impatiens glandulifera (Himalayan Balm) on processes that affect the filter and retention function of soils for copper, a regionally applied fungicide.Two soils, overgrown with the invasive I. glandulifera and by the native Urtica dioica were characterized for general soil properties and their copper retention ability assessed by a sequential extraction after seven days flooding with three different copper concentrations.We observed higher values for the absolute copper concentration in all fractions for the soil overgrown with I. glandulifera than for the soil overgrown with U. dioica. However, with respect to the total content, copper was more mobile in soil overgrown with U. dioica despite a higher organic matter content. The lower extraction recovery of the U. dioica soil suggests that more copper was mobilized in colloids which in long-term are easier washed out while I. glandulifera favors immobilization of organically chelated copper enhancing a legacy effect.Our results highlight the plant specific impact possibly induced by root exudates and plant residues affecting soil organic matter quality including the colloidal fraction and thus filter and retention functions of riparian soils.

Effects of drying-rewetting cycles on colloidal phosphorus composition in paddy and vegetable soils

The impact of drying-rewetting (DRW) cycles on soil phosphorus (P) behavior is well-established; however, its impact on the different-sized colloidal P (CP) in agricultural soils is still unclear. To investigate the effect of DRW events on the mobilization of CP in agricultural soils, and to understand how this impact varies with different DRW cycles and drought intensities, the study explored the role of soil type, CP fractions, and compositions. The concentration of CP was measured in paddy soil and vegetable soil after 3, 6, and 9 DRW cycles of varying intensities. The CP was then fractionated into fine-sized colloids (FC-P; 1–220 nm), medium-sized colloids (MC-P; 220–450 nm), and coarse-sized colloids (CC-P; 450–1000 nm) through soil supernatant filtration. CP accounted for 71.1 % and 55.6 % of water-dispersible colloidal P (<1000 nm) in paddy and vegetable soils, with FC-P constituting the greatest proportion at 50 % and 44 % of CP respectively. The colloidal fraction correlated with organic carbon, aluminum, and iron. DRW cycles did not change the overall distribution of the three CP size fractions. However, they affected the concentration and composition of CP. This study concluded that DRW can have significant implications for nutrient release and water quality in agricultural soils and that maintaining soil moisture at 50 % to 70 % of water-holding capacity could alleviate CP accumulation resulting from DRW cycles.

Spatial and temporal distribution of geochemical elements and their processes in different size fractions–Miri River (NW Borneo)

The toxicity, persistence, and propensity for accumulation of metals in aquatic environments have raised significant concerns globally. Expansion of urbanization with the growth of industrial and agricultural sectors in Miri City results in a high concentration of pollutants that flow directly into the Miri River. Hence, this study provides a comprehensive analysis of the Miri River water quality, focusing on spatial and temporal variations. River water samples were collected in two different time periods and analysed for physico-chemical parameters includes major ions, nutrients, metals and isotopes. Particularly, the metals were analysed in different size fractions (particulate and colloid) of the suspended solids. Geochemical plots, pollution index, geochemical modelling and factor analysis were used for the data analysis. Interpretation of data reveals that the mean concentration of metals in river water were increased from downstream to the upstream of the river irrespective of the seasons. Major ions were mostly derived from the chemical weathering of source rocks, which was supported by the Gibbs plot. Piper plot indicates the seasonal shifting of water types from Ca–Mg to Na–Cl. Isotopic signatures reveal direct atmospheric precipitation and evaporation were the major origins of river water. Fe was the dominant metal concentration in river water irrespective of the seasons (mean concentration 1.05 mg/L). Fe and Zn were the dominant metal concentration observed in all the 3 size fractions of suspended solids. Industrial activities and seawater influx dominate in the downstream, whereas weathering and agricultural inputs are significant in the upstream of the river. Particulate and colloidal fractions are the major contributors for the metal transport in the midstream and downstream of the river. The outcome of this study offer a thorough understanding of the seasonal elemental distribution at different size fractions, geochemical behaviour and the pollution status of the Miri River. With this knowledge, sustainable management strategies can be developed for this crucial water resource to the benefit of Miri community.

Organo-mineral associations and size-fractionated colloidal organic carbon dynamics in a redox-controlled wetland

The formation of organo-mineral associations serves as a crucial mechanism for stabilizing soil organic matter, particularly for determining the fate of soil organic carbon (OC) in redox dynamic wetlands characterized by high C content. Despite its importance, few studies have assessed the retention, transformation, and transport of colloids (1–1000 nm) and colloidal OC (COC) in those environments. This leaves a crucial knowledge gap concerning the quantities of colloids and COC and their molecular compositions, especially considering the significant role of metabolically active depressional wetlands that may play as biogeochemical hotspots for C cycling. To address this gap, we conducted a study in a Delmarva Bay depressional wetland located in Blackbird State Forest, Delaware, USA. We established a transect encompassing upland (U), transition (T), and wetland (W) zones based on seasonal hydrologic conditions. We installed piezometers at 50 cm, 100 cm, and 200 cm depths within each zone and collected pore-water samples from 11/2017 to 05/2019. We then fractionated these samples into dissolved (<2.3 nm), natural nanoparticle (NNP, 2.3–100 nm), fine colloid (100–450 nm), and particulate (450–1000 nm) fractions via sequential centrifugation and ultrafiltration, and quantified their concentration and molecular composition. We observed variations in the concentration and molecular composition of soil COC both vertically at different soil depths and horizontally along a redox gradient from the U-T-W transect. The sum of the NNP and fine colloid fractions accounted for 47±20% of the operationally defined “dissolved” (<450 nm) fraction. Isotope ratio mass spectrometry and X-ray photoelectron spectroscopy analyses further revealed that the NNP fraction is more enriched in heavier δ13C isotope and oxidized carbonyl/carboxyl C functional groups (C=O, p<0.05) with significantly higher surficial atomic percentages of C (p<0.01), N (p<0.01), and Mg:Al ratios (p<0.05), and lower atomic percentages of Al (p<0.01) and Si (p<0.01) compared to the larger particles. The formation of cation bridges and/or hydrogen bonds between carboxylic OC and phyllosilicate minerals likely dominated the mineral-OC association in the NNP fraction. The higher surface C enrichment in the particulate fraction compared to the NNP fraction suggests a patchy distribution of more plant-derived OC through organo-organic interactions in the larger fractions. Along the transect, Zone U exhibited significant enrichment of heavier δ13C isotope and lower SUVA values than the Zones T and W indicating inefficient decomposition and dissociation of SOM from minerals due to the reductive dissolution of Fe and Al oxides under anoxic conditions. Furthermore, an increase in low molecular weight microbial metabolites with reduced aromatic OC content was observed at deeper depths in Zones U and T. Our study provides new insights into the concentration and molecular composition of size-fractionated COC, highlighting the need to separately consider the NNP and fine colloid fractions from the operationally defined “dissolved” phase. This is crucial for assessing the biogeochemical cycling of OC in redox-active wetlands, a pressing need amidst the growing concerns about the impacts of climate change.

Cadmium and zinc isotope compositions indicate metal sources and retention mechanisms in different soil particle size fractions

Soil particle size may significantly affect metal distribution and stable isotopic behavior. Here, two soils were separated into four particle size fractions, namely fine sand, silt, fine silt, and colloidal particles and used to determine cadmium (Cd) and zinc (Zn) concentrations and isotope compositions. Concentrations of Cd and Zn were generally enriched in the finer particles and positively correlated with the iron (Fe) and manganese (Mn) oxide contents. However, Cd concentration in the fine sand was higher than in the silt fraction due to the higher soil organic matter contents in the former particle fraction. The maximum δ114/110Cd value was found in the colloidal particles (−0.02 and 0.01‰) of both soils while the minimum was in the silt particles (−0.12 and 0.06‰). Incorporation into the mineral lattice of Fe and Mn oxides is suggested to explain the slight enrichment of heavy Cd isotopes in the colloidal fraction. The similar δ66Zn values of the four particle fractions (0.20–0.29‰ with a mean of 0.25‰) indicate similar Zn sources in different particle sizes. Metal isotopic fingerprint of different soil particle size fractions provides further insight into the underlying metal retention mechanisms within soil micro-zones and helps in tracing metal sources and biogeochemical processes.

On the ac Measurements of the Electrical Conductivity of Dilute Colloidal Electrolytes

The details of ac-conductivity measurements in a colloidal electrolyte cell with flat control gate electrodes are discussed. The use of impedance diagnostics in studies of transport phenomena in such systems requires caution in the definition of the thickness of the screening accumulation layers that appear along the metal-electrolyte interfaces. The value of this characteristic length λ0 critically depends on the volume fraction ϕ⊙ of colloidal particles in the bulk of the electrolyte. Accounting for the dependence λ0(ϕ⊙) makes it possible to consistently explain the large discrepancy in the available experimental data regarding the influence of the colloidal fraction on the effective conductivity of the colloidal suspension.

Does anoxia promote the mobilization of P-bearing colloids from dam reservoir sediment?

In the context of a reservoir, the anoxia that develops in the bottom sediment induces the release of phosphorus (P) into the overlying water, thus supporting eutrophication. Most studies focusing on P dynamic in an aquatic environment fail to consider the “truly” dissolved and colloidal fractions, hence the colloidal P has gone largely unexplored. The aim of this study was to investigate the release of sedimentary P under oscillating aerobic, anoxic and aerobic conditions, in taking into account the colloidal (10 kDa–1 µm) and truly dissolved (< 10 kDa) fractions. Laboratory incubations of wet sediment originating from a dam reservoir were performed over 63 days, consisting of 25 days of aerobic conditioning (lasting 2 periods) and 38 days of anoxia. Results showed that oxic conditions induced a very limited release of phosphorus, both in truly dissolved and colloidal forms. In turn, the development of anoxic conditions caused a large release of P, mainly in the colloidal fraction, representing about 90 % of the total water-mobilizable P (PWM < 1 µm). The initial release of truly dissolved P during the anoxic stage gradually diminished over time, possibly due to the formation of secondary minerals or re-adsorption processes. Approximately half of the PWM released during anoxia persisted under subsequent oxic conditions and consisted solely of colloidal P. The dynamics of PWM were primarily influenced by two main factors: (i) the reductive dissolution of iron, which released both dissolved and colloidal P, and (ii) the release of indigenous organic matter, which impacted the stability of the released colloids through bridging mechanisms.

Novel details on the dissociation of casein micelle suspensions as a function of pH and temperature

Membrane filtration is a widespread process for fractionation and recombination of milk components. Although the dissociation of micellar caseins has been studied in detail in skim milk, it is important to better understand the dissociation dynamics occurring between the colloidal and noncolloidal fractions in systems of modified composition. This research aimed at understanding the dissociation of casein proteins in micellar fractions depleted of whey proteins. Casein micelle dispersions were tested at neutral pH and pH 6 (using glucono-δ-lactone as acidulant), after incubation at 4°C or 22°C, and compared with skim milk. The ionic composition of the serum phase was measured using inductively coupled plasma-mass spectrometry, and the protein distribution analyzed using reversed phase-HPLC coupled with mass spectrometry. When incubated at 22°C, there were no differences in casein micelle dissociation between skim milk and whey protein-depleted micelles (∼2.6% dissociated casein). No additional dissociation occurred by lowering the pH from 6.8 to 6 at 22°C, albeit there were more soluble ions at low pH (71% Ca and 65% P). At 4°C, there was an increased amount of β-casein found in the serum phase (23-33% of total β-casein). In addition, there was an uneven dissociation behavior of the various genetic β-casein variants, whereof A2 was more readily released with cooling. In skim milk, approximately 22%, 18%, and 14% of κ-, αS2, and αS1-caseins, respectively, were dissociated from the micellar phase upon cooling and acidification to pH 6.0. This was in contrast to whey protein-depleted casein suspensions, in which only 6%, 5%, and 3% of κ-, αS2, and αS1-caseins, respectively, had dissociated. The results suggested that the whey proteins in the serum phase play a role in the equilibrium between colloidal and soluble caseins in milk. This is of great relevance in processes such as cold membrane fractionation, where more attention should be given to the protein composition in the serum phase, especially when concentration is combined with fractionation of the serum proteins.

Long-term missing role of small colloids and nanoparticles on the loading and speciation of phosphorus in catfish aquaculture ponds in west Alabama

Increasing loading of phosphorus (P) into freshwater systems is deemed as one of the key drivers triggering harmful algal blooms (HABs). However, conventional water quality monitoring of P normally uses the operational cutoff (e.g., 450-nm filter membrane) to separate particulate and dissolved phases (entities passing through the 450-nm membrane are regarded as dissolved phase), which completely neglects the roles of small colloids (450–100 nm) and nanoparticles (100–1 nm). Herein, a new particle size separation approach was used to separate water samples collected from catfish aquaculture ponds in west Alabama into six size fractions: large particles (>1000 nm), large colloids (1000–450 nm), small colloids (450–100 nm), large nanoparticles (100–50 nm), small nanoparticles (50–1 nm), and the truly dissolved phase (<1 nm). The speciation and concentration of P in these six size fractions were then investigated using Hedley's sequential extraction method. The new particle size separation results showed that particle loading (mass) followed the order: >1000 nm, 450–100 nm, 1000–450 nm, 100–50 nm, and 50–1 nm. This is mainly due to the abundance of large-sized (>1000 nm) zooplankton and phytoplankton such as algae and cyanobacteria in the catfish aquaculture ponds. Importantly, the small colloid (450–100 nm) and nanoparticle (100–1 nm) size fractions, which were previously regarded as the dissolved phase using the 450-nm membrane filtration operation, accounted for ∼41.8% of the total particle mass. The Hedley's sequential extraction results showed that sodium hydroxide (NaOH)-extracted P represented the largest P pool, followed by water (H2O)- and sodium bicarbonate (NaHCO3)-extracted P pools. Smaller particles exhibited a higher loading of P due to their large surface areas. These new findings suggest that the new particle size separation approach needs to be adopted for future water quality monitoring and mitigation of HABs in freshwater ecosystems.

Transfer of 129I to freshwater fish species within Fukushima and Chernobyl exclusion zones

Unique data is reported on the transfer of 129I iodine from freshwaters to fish as well as the internal distribution within fish from the Fukushima and Chernobyl exclusion zones (ChEZ). Samples of water, sediments and fish were collected in the contaminated ponds Inkyozaka and Suzuuchi, and in the less contaminated Abukuma river in Fukushima, as well as in the contaminated Glubokoye lake and in the less contaminated Starukha lake in ChEZ. In water, 129I was mainly present as low molecular mass (LMM) and negatively charged species, while a minor fraction was associated with colloidal fraction, most probably organic material in water. The sediment-water 129I apparent distribution coefficients, Kd, ranged from 225 to 329 L/kg, equal that of stable iodine, but did not correlate with 129I/127I ratio or 129I/137Cs ratio as the environmental distribution of radioactive iodine was different from that of stable iodine and radioactive cesium. Concentration ratios (CR) of 129I in muscle of freshwater fish ranged from 85 to 544 across waterbodies with limited water exchange, similar in Fukushima and Chernobyl, but varied with respect to fish species. Thus, this is the first results on the transfer of 129I to freshwater fish, showing that the CR for freshwater fish is higher than CR reported for marine fish. Concentrations of 129I in fish muscle were, however, lower than in the intestinal content, indicating the influence of more contaminated dietary ingredients probably of terrestrial origin based due to δ13C signal on as well as of biodilution. The present results highlighted also that the radiation dose in fish was highly inhomogeneously distributed. Based on the present 129I/127I atomic ratio of 10−5 in the most contaminated fish in the ponds in Fukushima and Glubokoye lake in Chernobyl, however, a radiation dose of 10 μSv/y would not pose any harm to the fish population.

Novel insights into the mechanisms for Sb mobilization in groundwater in a mining area: A colloid field study

Colloids may play an important role in the geochemical cycle of antimony (Sb). However, the controlling behaviors of colloids on Sb fate in contaminated groundwater are not available. To investigate the effects of colloids on Sb mobility, groundwater samples from Xikuangshan Sb Mine's two main aquifers (the D3s2 aquifer and the D3x4 aquifer) were successively (ultra)filtered through progressively decreasing pore sizes (0.45 µm, 100 kDa, 50 kDa and 5 kDa). The results showed that 0.1–84.1% of Sb was adsorbed or carried by colloids, which corresponded to Sb concentration ranging between 0 and 2973 μg/L in the colloids (0.45 µm - 5 kDa). In both aquifers, Sb was closely associated with organic colloids (r = 0.72 p < 0.05 for the D3x4 aquifer, r = 0.94 p < 0.01 for the D3s2 aquifer). Parallel factor analysis of the three-dimensional fluorescence spectra determined that the protein-like substances in the D3x4 aquifer and the humus-like substances in the D3s2 aquifer controlled Sb behavior. X-ray absorption spectroscopy confirmed Sb complexing with organic substances. Competitive adsorption of As and Sb suppressed the complexation of colloids with Sb, particularly in the D3x4 aquifer (r = –0.71, p < 0.05). Sb mobility was also influenced by the redox of the groundwater system. As the oxidation-reduction potential and dissolved oxygen increased, Sb in the colloidal fractions decreased. These findings provide new insights into the mechanisms involved in Sb fate affected by colloids, establishing the theoretical basis for developing effective Sb and even metalloid pollution remediation strategies.

Coupling effect of solvent–colloid interaction on diffusivity and viscosity of colloidal hard-sphere suspensions: Statistical mechanical free-volume approach

Apart from describing the transport behaviors to a reliable accuracy, it remains as yet far from satisfactory to comprehend the explicit role of the solvent–colloid interaction on the diffusivity and viscosity of colloidal hard-sphere suspensions. Here, we exploit the free volume effect on the diffusivity and viscosity by means of statistical mechanics, which enables to express them in terms of the solvent–solvent, colloid–colloid, and solvent–colloid pair correlation functions as a function of the colloidal concentration. The agreement between the theory and experiment is found to be very good over the entire colloidal volume fraction ϕ investigated by experiment, i.e., up to ϕ∼0.60. The present theory predicts a crossover in the solvent effect on the diffusivity: Above ϕc=0.38, the solvent–colloid interaction enhances the diffusivity of the colloidal particles suspended therein, whereas below ϕc, it serves as a diffusion barrier against the particles.

Assessment of nanoplastic extraction from natural samples for quantification purposes

Plastic pollution poses an increasing threat to the whole ecosystem. Scientists recently realized that this pollution also occurs at the nanoscale. Nanoplastic monitoring is a real challenge and published data are scarce. Above the use of appropriate analytical instrument, one main obstacle is to quantitatively isolate the nanoplastic from larger particles in real samples. We propose a method based on the monitoring of polystyrene nanospheres following the polystyrene intrinsic fluorescence to assess the losses. Polymer-based membranes were tested for filtration, ultrafiltration and dialysis; important losses were observed. The isolation of the colloidal fraction is proposed using stainless steel grid with reduction of the losses. The ability of glass fiber filters to trap the nanoplastic was also evaluated as a mean to transfer the particle to the analytical instrument. As an illustration, a river sample was processed with the recommended protocol and the colloidal content monitored by nanoparticle tracking analysis. As a conclusion, we insist on the fact that it is absolutely necessary to evaluate nanoplastic extraction efficiencies for quantification purposes and we give recommendations to limit losses.

Iron colloidal transport mechanisms and sequestration of As, Ni, and Cu along AMD-induced environmental gradients

Colloids are common in mine waters and their chemistry and interactions are critical aspects of metal(loid)s cycling. Previous studies mostly focus on the colloidal transport of metal(loid)s in zones where rivers and soil profiles receive acid mine drainage (AMD). However, there is limited knowledge of the colloid and the associated toxic element behavior as the effluent flows through the coal waste dump, where a geochemical gradient is produced due to AMD reacting with waste rocks which have high acid-neutralization effects. Here, we investigated the geochemistry of Fe and co-occurring elements As, Ni, and Cu along the coal waste dump, in aqueous, colloidal, and precipitate phases, using micro/ultrafiltration combined with STEM, AFM-nanoIR, SEM-EDS, XRD, and FTIR analysis. The results demonstrated that a fast attenuation of H+, SO42−, and metal(loid)s happened as the effluent flowed through the waste-rock dump. The Fe, As, Ni, and Cu were distributed across all colloidal sizes and primarily transported in the nano-colloidal phase (3 kDa–0.1 μm). An increasing pH induced a higher percentage of large Fe colloid fractions (> 0.1 μm) associated with greater sequestration of trace metals, and the values for As from 39.5 % to 54.4 %, Ni from 40.8 % to 75.7 %, and Cu from 43.7 % to 56.0 %, respectively. The Fe-bearing colloids in AMD upstream (pH ≤ 3.0) were primarily composed of Fe–O–S and Fe–O–C with minor Al–Si–O and Ca–O–S, while in less acidic and alkaline sections (pH ≥ 4.1), they were composed of Fe–O with minor Ca–O–S. The iron colloid agglomerates associated with As, Ni, and Cu precipitated coupling the transformation of jarosite, and schwertmannite to ferrihydrite, goethite, and gypsum. These results demonstrate that the formation and transformation of Fe-bearing colloids response to this unique geochemical gradient help to understand the natural metal(loid)s attenuation along the coal waste dump.

Assessment of 226Ra and U colloidal transport in a mining environment

The colloidal transport of trace (Fe, Al, Ba, Pb, Sr, U) and ultra-trace (226Ra) elements was studied in a mining environment. An original approach combining 0.45 μm filtered water sampling, the Diffusive Gradient in Thin films (DGT) technique, mineralogical characterization, and geochemical modelling was developed and tested at 17 sampling points. DGT was used for the truly dissolved fraction of the elements of interest, while the 0.45 μm filtration includes both colloidal and truly dissolved fractions (together referred to as total dissolved fraction). Results indicated a colloidal fraction for Al (up to 50%), Ba (up to 86%), and Fe (up to 99%) explained by the presence of submicrometric grains of kaolinite, barite, and ferrihydrite, respectively. Furthermore, the total dissolved 226Ra concentration in the water samples reached up to 10–25 Bq/L (1.2–3.0 10−12 mol/L) at 3 sampling points, while the truly dissolved aqueous 226Ra concentrations were in the mBq/L range. Such high total dissolved concentrations are explained by retention on colloidal barite, accounting for 95% of the total dissolved 226Ra concentration. The distribution of 226Ra between the truly dissolved and colloidal fractions was accurately reproduced using a (Rax,Ba1-x)SO4 solid solution, with values of the Guggenheim parameter a0 close to ideality. 226Ra sorption on ferrihydrite and kaolinite, other minerals well known for their retention properties, could not explain the measured colloidal fractions despite their predominance. This illustrates the key role of barite in such environments. The measured concentrations of total dissolved U were very low at all the sampling points (<4.5 10−10 mol/L) and the colloidal fraction of U accounted for less than 65%. U sorption on ferrihydrite could account for the colloidal fraction. This original approach can be applied to other trace and ultra-trace elements to complement when necessary classical environmental surveys usually performed by filtration on 0.45 μm.

Role of colloids in the transfer and dispersion of trace elements into river waters through a former mining district

Characterizing the different chemical forms of trace elements in surface inland waters of mining regions is very important to understand the mechanisms underlying metal(loid) transport, their accumulation and toxicity, especially when waste storage areas are closely linked to the hydrographic network. This study focuses on the oldmining district of Salsigne in the Orbiel Valley (France), which was at one time the largest gold mine in Europe and the world’s largest arsenic mine. Our objective was to better understand the factors governing the transport of As and to investigate the role of colloidal matter as vector of major (Al, Ca, Fe, Mg) and trace (As, Pb, REE) elements in waters.A field sampling campaign was carried out during high water season to collect samples from the Orbiel River and its tributaries. In situ (ultra)filtrations at different cut-off thresholds (0.22 μm, 0.025 μm, 100 kDa and 3 kDa) were performed and physicochemical parameters (conductivity, pH, alkalinity, Dissolved Organic Carbon: DOC, anions, major cations, and metal(loid)s concentrations) of river water were assessed in all fractions.Results showed decreasing concentrations of DOC, Fe, Al and REE in the conventionally dissolved fraction (< 0.22 μm) from upstream to downstream. Arsenic concentration increased from upstream to downstream, especially at the exit of the old mining zone, and was mainly present in the truly dissolved fraction. However, arsenic in the colloid fraction was about 40% upstream and showed a clear decrease when going downstream. Upstream, Fe and Al were mostly present in the colloidal fraction (around 90%, but decreased to 30% downstream for Al). REE patterns suggested that colloidal organic matter played a significant role in metal transport. This was also inferred from the greater enrichment in middle REE as compared to light and heavy REE; this difference in enrichment progressively disappeared with decreasing cut-off filter size. The concentration variations along the length of the river were found to be a combined effect of the changes in lithology and input of contaminants from storage areas or alluvial table.

Abundance of colloidal organic phosphorus in the Taiwan Strait

The Taiwan Strait is a coastal sea with dynamic hydrologic condition and dissolved organic matter (DOM) cycling. To better understand its phosphorus (P) transformation, phosphate and bulk dissolved organic phosphorus (DOP) concentrations were determined in the surface water of the Taiwan Strait during 2010 and 2011 summers. The bulk DOP was further fractionated into the low molecular weight (LMW) DOP and colloidal organic phosphorus (COP) with the application of the cross-flow ultrafiltration technique at a size cut-off of 10 kDa. The surface water in the Taiwan Strait generally showed higher bulk DOP concentration than phosphate excluding estuarine stations. This is similar to the surface waters in the subtropical gyres, implying a P-deficient condition in the Taiwan Strait. The LMW-DOP followed a constant permeation behavior in the ultrafiltration experiments, allowing the quantification of LMW-DOP and COP concentrations with the ultrafiltration permeation model. The average COP concentration was 0.044 ± 0.022 μmol/L and 0.042 ± 0.027 μmol/L during 2010 and 2011 summers, respectively. Accordingly, COP accounted for 35 ± 13% and 34 ± 16% of bulk DOP during 2010 and 2011 summers, respectively, suggesting a substantial occurrence of organic phosphorus in the colloidal fraction. The C/P ratio decreased from LMW-DOM to bulk DOM and to colloidal organic matter (COM), supporting the degradation pathway of bulk DOM from colloidal to LMW fractions and the lability of COP in the Taiwan Strait. The fractionation of C/P ratio between bulk DOM and COM in the Taiwan Strait, denoted by the fractionation factor (FC/D), was comparable to the open oceans, but significantly stronger than rivers and estuaries. It might indicate an autochthonous input and rapid turnover of bulk DOP pool in the Taiwan Strait in the context of low phosphate concentration. The FC/D also showed a spatial variability in the Taiwan Strait, high in the South China Sea Warm Current and upwelling occupied stations and low in inshore areas influenced by terrestrial input. This further supports the FC/D as an indicator of bulk DOM sources besides its application to decipher the diagenetic status of bulk DOM and biogeochemical cycles of bulk DOP in the coastal oceans.

Effect of the Added Acyl Homoserine Lactones on Separated Free-Living Marine Bacteria as a Model of Quorum Sensing

Quorum sensing is a communication system by which bacteria use signal molecules to induce a physiological response. In natural marine environments, quorum sensing is suspected to occur in regions with high cell densities. Free-living bacteria, however, are largely believed to exist at concentrations too low to make use of a density-dependent quorum-sensing system. Due to so-called ‘free-living’ bacteria inhabiting marine gels composed of exopolymeric substances occurring in an operationally defined colloidal fraction, it is possible that quorum-sensing molecules would also occur in this fraction. In this study, possible signaling molecules were collected from marine water, separated, and concentrated as some organic matter. Their identification with an Agrobacterium tumefaciens assay indicated the presence of AHLs. In fall 2002 and spring 2003, free-living (single cells) fraction of marine bacterioplankton was sampled and separated. Various AHLs were added to these disperse populations (109 cells/L). The studied bacterial communities responded with change in the thymidine incorporation. The results are discussed as existence of active reaction of marine free-living bacteria to signaling molecules even in sparse inhabiting marine gels. That there is a bacterial response to signaling molecules in so sparse populations is of great significance for marine and environmental sciences.