Trace elements in organic- and iron-rich surficial fluids of the boreal zone: Assessing colloidal forms via dialysis and ultrafiltration

On-site size fractionation of about 40 major and trace elements (TE) was performed on waters from boreal small rivers and their estuaries in the Karelia region of North-West Russia around the “Vetreny Belt” mountain range and in Paanajärvi National Park (Northern Karelia). Samples were filtered in the field using a progressively decreasing pore size (5 μm, 2.5 (3) μm, 0.22 (0.45) μm, 100 kDa, 10 and 1 kDa) by means of frontal filtration and ultrafiltration (UF) techniques and employing in-situ dialysis with 10 and 1 kDa membranes followed by ICP-MS analysis. For most samples, dialysis yields a systematically higher (factor of 2-3) proportion of colloidal forms compared to UF. Nevertheless, dialysis is able to provide a fast and artefact-free in-situ separation of colloidal and dissolved components.Similar to previous studies in European subarctic zones, poor correlation of iron concentration with that of organic carbon (OC) in (ultra)filtrates and dialysates reflect the presence of two pools of colloids composed of organic-rich and Fe-rich particles. All major anions and silica are present as dissolved species (or solutes) passing through the 1-kDa membrane. Size-separation ultrafiltration experiments show the existence of larger or smaller pools of colloidal particles different for each of the considered elements.The effect of rock lithology (acidic versus basic) on the colloidal speciation of TE is seen solely in the increase of Fe and some accompanying TE concentrations in catchment areas dominated by basic rocks compared to granitic catchments. Neither the ultrafiltration pattern nor the relative proportions of colloidal versus truly dissolved TE are affected by the lithology of the underlying rocks: within ±10% uncertainty, the two colloidal (10 kDa-0.22 μm and 1-10 kDa) and the truly dissolved (<1 kDa) pools show no difference in percentage of TE distribution between two types of bedrock lithology. The same conclusion is held for organic- and Fe-rich waters. In contrast, landscape context analysis demonstrated slight dominance, for most TE affected by UF, of large-size colloids (10 kDa-0.22 μm) in rivers and streams and small-size colloids and truly dissolved fractions in swamp stagnant surface waters. This supports the existence of two pathways of colloids formation: during the plant litter degradation in wetland zones and at the redox front in river riparian zone.     

Flood zone biogeochemistry of the Ob River middle course

The flood zone of the Ob River, the largest (in watershed area) river of the Arctic Ocean basin, is tens of km wide and, after the Amazon's Varzea, is the world's second largest flooding territory. To better understand the biogeochemistry of the Ob River and adjacent surface waters, we studied, in May and July 2014, the dissolved and colloidal organic carbon and trace metals in small rivers, lakes, and flooded water bodies connected and disconnected with the mainstream as well as the Ob River itself. All major and trace elements were distributed among two major categories depending on their pattern of dependence on the dissolved organic carbon (DOC) concentration. Dissolved inorganic carbon (DIC), Na, Mg, Ca, sulfate, Sr, Mo, Sb and U exhibited a general decrease in concentration with the increase of the [DOC]. The lowest concentration of these elements was observed in DOC-rich humic, acidic (4.9 ≤ pH ≤ 6.1) upland lakes fed by surrounding bogs. These elements marked the influence of underground feeding in July during summer baseflow, which was most visible in flood lakes in the Ob riparian zone and the Ob River itself. In May, the flood lakes were statistically similar to the Ob River. The elevated concentration of DOC (up to 60 mg/L) in the upland lakes was not correlated with groundwater-related elements, suggesting a lack of significant groundwater feeding in these lakes. In contrast, insoluble, usually low mobile elements (Al, Fe, other trivalent hydrolysates, Ti, Zr, Hf) and some metals (Cr, Zn, Ni, Pb) demonstrated a steady increase in concentration with increasing DOC, with the lowest values observed in the Ob River and the highest values observed in small tributaries and organic-rich upland lakes in July. It follows that these elements are limited by their main carriers – organic and organo-ferric colloids, rather than by the availability of the source, peat and mineral soil or plant litter. While for the majority of non-colloidal, groundwater-fed elements with high mobility (DIC, Na, Mg, Ca, K, Sr…) the small tributaries can be used as representatives of the Ob main stream, this is not the case for low mobility “insoluble” elements, such as Fe, Al, trivalent and tetravalent hydrolysates, and metal micronutrients (Cu, Zn, and Mn). The low soluble elements and divalent metals exhibited a much lower concentration in the river mainstream compared to that in the flood lakes, upland lakes and small rivers. This difference is significantly more pronounced in the baseflow in July compared to the spring flood in May. Presumably, autochthonous processes, such as the photo-oxidation and bio-oxidation of organo-ferric colloids and phytoplankton uptake are capable decreasing the concentration of these elements in the river mainstream.     

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.     

Seasonal variability of element fluxes in two Central Siberian rivers draining high latitude permafrost dominated areas

In order to constrain the origin and fluxes of elements carried by rivers of high latitude permafrost-dominated areas, major and trace element concentrations as well as Sr and U isotopic ratios were analyzed in the dissolved load of two Siberian rivers (Kochechum and Nizhnyaya Tunguska) regularly sampled over two hydrological cycles (2005-2007). Large water volumes of both rivers were also collected in spring 2008 in order to perform size separation through dialysis experiments. This study was completed by spatial sampling of the Kochechum watershed carried out during summer and by a detailed analysis of the main hydrological compartments of a small watershed. From element concentration variations along the hydrological cycle, different periods can be marked out, matching hydrological periods. During winter baseflow period (October to May) there is a concentration increase for major soluble cations and anions by an order of magnitude. The spring flood period (end of May-beginning of June) is marked by a sharp concentration decrease for soluble elements whereas dissolved organic carbon and insoluble element concentrations strongly increase.When the spring flood discharge occurs, the significant increase of aluminum and iron concentrations is related to the presence of organo-mineral colloids that mobilize insoluble elements. The study of colloidal REE reveals the occurrence of two colloid sources successively involved over time: spring colloids mainly originate from the uppermost organic-rich part of soils whereas summer colloids rather come from the deep mineral horizons. Furthermore, U and Sr isotopic ratios together with soluble cation budgets in the Kochechum river impose for soluble elements the existence of three distinct fluxes over the year: (a) at the spring flood a surface flux coming from the leaching of shallow organic soil levels and containing a significant colloidal component (b) a subsurface flux predominant during summer and fall mainly controlled by water-rock interactions within mineral soils and (c) a deep groundwater flux predominant during winter which enters large rivers through unfrozen permafrost-paths. Detailed study of the Kochechum watershed suggests that the contribution of this deep flux strongly depends on the depth and continuous nature of the permafrost.     

Changes in size distribution of fresh water nanoscale colloidal matter and associated elements on mixing with seawater

Changes in size distribution and elemental composition of 0.5-50 nm fresh water colloids during estuarine mixing have been studied by in-laboratory mixing of natural creek water and synthetic seawater, followed by size fractionation with Asymmetrical Flow Field-Flow Fractionation, and online elemental quantification by High-Resolution ICPMS. At least two types of colloids were present in the studied size region; 0.5-3 nm fluorescent dissolved organic matter (FDOM), and >3 nm colloids that were rich in Fe and colored dissolved organic matter (CDOM). Most trace elements were associated in different proportions to these two populations of colloids. Following mixing with synthetic seawater, the >3 nm Fe-rich colloids and CDOM were extensively removed from the studied size region by salt induced aggregation. The degree of removal with increasing salinity was greatest below 2.5‰ salinity, continued to a lesser degree between 2.5‰ and 15‰ salinity, above which only very small additional removal could be distinguished. At 25‰ salinity, the Fe concentration in the 0.5-50 size region had been reduced down to 15% of its original value in freshwater, while the amount of CDOM had been reduced to 55%. On the contrary, the concentration of the 0.5-3 nm FDOM was unchanged by the increased concentration of sea salt. Therefore, colloidally associated Al, P, Co, Cu, Zn, Ce, Lu and Pb were removed from the 0.5-50 nm size region according to their relative distributions between the FDOM and the Fe-rich colloids. Consequently, at 25‰ salinity, the 0.5-50 nm concentrations of Al, Mn, P and Pb, (mainly associated with the Fe-rich colloids) had been reduced down to 13-26 % of their values in freshwater, while the concentrations of Co and Cu (with higher preferences for FDOM) were less reduced, down to 46% and 57%, respectively. Changes in the elemental composition of the remaining colloidal matter were observed, the most pronounced were increased contents of P, Al and Pb in Fe-rich colloidal matter of medium size (∼3-15 nm) and increased Pb content in Fe-rich colloidal matter of larger size (∼5-50 nm).     

Iron colloids/organic matter associated transport of major and trace elements in small boreal rivers and their estuaries (NW Russia)

The chemical status of major and trace elements (TE) in various boreal small rivers and watershed has been investigated along a 1500-km transect of NW Russia. Samples were filtered in the field through a progressively decreasing pore size (5, 0.8 and 0.22 μm; 100, 10, and 1 kD) using a frontal filtration technique. All major and trace elements and organic carbon (OC) were measured in filtrates and ultrafiltrates. Most rivers exhibit high concentration of dissolved iron (0.2–4 mg/l), OC (10–30 mg/l) and significant amounts of trace elements usually considered as immobile in weathering processes (Ti, Zr, Th, Al, Ga, Y, REE, V, Pb). In (ultra)filtrates, Fe and OC are poorly correlated: iron concentration gradually decreases upon filtration from 5 μm to 1 kD whereas the major part of OC is concentrated in the <1–10 kD fraction. This reveals the presence of two pools of colloids composed of organic-rich and Fe-rich particles. According to their behavior during filtration and association with these two types of colloids, three groups of elements can be distinguished: (i) species that are not affected by ultrafiltration and are present in the form of true dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, Si, B, As, Sb, Mo) or weak organic complexes (Ca, Mg, Sr, Ba), (ii) elements present in the fraction smaller than 1–10 kD prone to form inorganic or organic complexes (Mn, Co, Ni, Zn, Cu, Cd, and, for some rivers, Pb, Cr, Y, HREE, U), and (iii) elements strongly associated with colloidal iron in all ultrafiltrates (P, Al, Ga, REE, Pb, V, Cr, W, Ti, Ge, Zr, Th, U). Based on size fractionation results and taking into account the nominal pore size for membranes, an estimation of the effective surface area of Fe colloids was performed. Although the total amount of available surface sites on iron colloids (i.e., 1–10 μM) is enough to accommodate the nanomolar concentrations of dissolved trace elements, very poor correlation between TE and surface sites concentrations was observed in filtrates and ultrafiltrates. This strongly suggests a preferential transport of TE as coprecipitates with iron oxy(hydr)oxides. These colloids can be formed on redox boundaries by precipitation of Fe(III) from inflowing Fe(II)/TE-rich anoxic ground waters when they meet well-oxygenated surface waters. Dissolved organic matter stabilizes these colloids and prevents their aggregation and coagulation. Estuarine behavior of several trace elements was studied for two small iron- and organic-rich rivers. While Si, Sr, Ba, Rb, and Cs show a clear conservative behavior during mixing of freshwaters with the White sea, Al, Pb and REE are scavenged with iron during coagulation of Fe hydroxide colloids.     

Colloidal arsenic composition from abandoned gold mine tailing leachates in Nova Scotia,Canada

Asymmetric-Flow Field-Flow Fractionation (AsFlFFF) coupled to an inductively coupled plasma-mass spectrometer (ICP-MS) was used to determine whether colloidal As exists in mine tailings from abandoned Au mine sites in Nova Scotia. Using this technique, the chemical composition and the size of the colloidal material was determined. Tailings samples were collected from the sites and leachates were analyzed. The resulting fractograms showed the presence of colloidal As. Arsenic co-elutes with Fe and Al suggesting that the As is associated with colloids containing these elements. The colloidal material present in the samples has a calculated median size of 7 nm. The leachates were also analyzed for totalAs, Fe and Al using ICP-MS. The colloidal fraction was determined to account for approximately 20% of the total dissolved As present in these samples. Dissolved As concentrations at the selected mine sites are very high and the arbitrary cutoff for dissolved still incorporates colloidal material. Therefore. it is important to distinguish between truly dissolved and colloidal As as the speciation will affect the toxicity and mobility of As at these locations.     

Colloid formation and metal transport through two mixing zones affected by acid mine drainage near Silverton,Colorado

Stream discharges and concentrations of dissolved and colloidal metals (Al, Ca, Cu, Fe, Mg, Mn, Pb, and Zn), SO₄, and dissolved silica were measured to identify chemical transformations and determine mass transports through two mixing zones in the Animas River that receive the inflows from Cement and Mineral Creeks. The creeks were the dominant sources of Al, Cu, Fe, and Pb, whereas the upstream Animas River supplied about half of the Zn. With the exception of Fe, which was present in dissolved and colloidal forms, the metals were dissolved in the acidic, high-SO₄ waters of Cement Creek (pH 3.8). Mixing of Cement Creek with the Animas River increased pH to near-neutral values and transformed Al and some additional Fe into colloids which also contained Cu and Pb. Aluminium and Fe colloids had already formed in the mildly acidic conditions in Mineral Creek (pH 6.6) upstream of the confluence with the Animas River. Colloidal Fe continued to form downstream of both mixing zones. The Fe- and Al-rich colloids were important for transport of Cu, Pb, and Zn, which appeared to have sorbed to them. Partitioning of Zn between dissolved and colloidal phases was dependent on pH and colloid concentration. Mass balances showed conservative transports for Ca, Mg, Mn, SO₄, and dissolved silica through the two mixing zones and small losses (<10%) of colloidal Al, Fe and Zn from the water column.     

Geochemistry of Major Elements in a Pristine Boreal River System; Hydrological Compartments and Flow Paths

Once or twice weekly, water sampling was undertaken for a two and a half year period in the Kalix River, northern Sweden. Soil water, groundwater, water in tributaries and mire water were also sampled at several occasions. Samples were filtered and analysed for major dissolved elements and TOC. Although only 5 of the bedrock in the Kalix River drainage basin is situated in the Caledonian mountains (mostly schist, with some outcrops of dolomite and limestone), the chemical composition of the river, at the river mouth, is clearly influenced by water from the mountain areas. High dissolved Ca/Mg ratios in June and July indicate a large influence of water from the mountain areas during summer. The dissolved Si/Mg ratio increases when water from the woodland (bedrock consisting of Precambrian granitoids) predominates during snowmelt in May, but the ratio is low during summer when water from the mountains is increased. However, the low Si concentrations in the mountain areas are probably not primarily the result of the different rocks but more a reflection of the less intense weathering of silicate minerals in the mountains. High Si/Mg ratios are closely related to high TOC. All the major dissolved elements, except TOC, are diluted by snowmelt in May. However, the dilution varies for different elements. Based on the interpretations of major element ratios the melt water discharge in May reflects two major compartments in the woodland; peatland areas and the upper section of the soil. During summer and autumn storm events in the woodland most of the storm water originated from peatland. High K/Mg ratios in the river in May are related to water discharge from the upper section of the till. Low S/Mg ratios in the river indicate an influence of mire water from the woodland both during melt water discharge in May and during increased water discharge in autumn. The Ca/Mg ratios in tributaries in the woodland are consistently lower during melt water discharge compared with values in August. The lower Ca/Mg ratio in May probably reflects water that has been in contact with the B-horizon in the till during spring flood. Data show that the TOC discharged during spring flood originates from two major compartments in the landscape, the upper soil profile and peatland. Storm discharge of TOC during the rest of the year originates mostly from peatland.     

The mechanism of iron removal in estuaries

A survey of U.S. east coast estuaries confirms that large-scale rapid removal of iron from river water is a general phenomenon during estuarine mixing. The river-borne ‘dissolved’ iron consists almost entirely of mixed iron oxide-organic matter colloids, of diameter less than 0.45 μm, stabilized by the dissolved organic matter. Precipitation occurs on mixing because the seawater cations neutralize the negatively charged iron-bearing colloids allowing flocculation. The process has been duplicated in laboratory experiments using both natural filtered and unfiltered river water and a synthetic colloidal goethite in 0.05 μm filtered water. The colloidal nature of the iron has been further confirmed by ultracentrifugation and ultrafiltration. A major consequence of the precipitation phenomena is to reduce the effective input of ‘dissolved’ iron to the ocean by about 90% of the primary river value, equivalent to a concentration of less than 1 μmol per liter of river water.     

Association of dissolved radionuclides released by the Chernobyl accident with colloidal materials in surface water

The association of dissolved ⁹⁰Sr, ^239,240Pu and ²⁴¹Am with natural colloids was investigated in surface waters in the Chernobyl nuclear accident area. A 4-step ultrafiltration (UF) study (<1 kilodaltons (Da), 1–10 kDa, 10–100 kDa, 100 kDa<) showed that 49–83% of ^239,240Pu and 76% of ²⁴¹Am are distributed in colloids of the two size fractions larger than 10 kDa (nominal molecular weight limit of the filter, NMWL), while ⁹⁰Sr was found exclusively (85–88%) in the lowest molecular size fraction below 1 kDa (NMWL) for the Sahan River water at the highly contaminated area close to the Chernobyl Nuclear Power Plant (ChNPP). Consistent results were obtained by 2-step fractionation (larger than and smaller than 10 kDa (NMWL)) for river and lake waters including other locations within about 30 km away from ChNPP. It is likely that Pu and Am isotopes were preferentially associated with dissolved organic matter of high molecular size, as suggested by the fact that (i) only a few inorganic elements (Mg, Ca, Sr, Si, Mn, Al) were found in the colloidal size ranges, and (ii) the positive correlation between dissolved organic C (DOC) concentrations and UV absorbance at 280 nm, a broad absorption peak characteristic of humic substances (HS) was found. A model calculation on the complexation of Pu and Am with HS as an organic ligand suggests that the complexed form could be dominant at a low DOC concentration of 1 mgC L⁻¹, that is commonly encountered as a lower limit in fresh surface water. The present results suggest the general importance of natural organic colloids in dictating the chemical form of actinides in the surface aquatic environment.     

西江流域梧州站干支流洪水组成及遭遇规律分析

为分析西江流域灾害性洪水的风险,采用水文学分析法从洪水组成、遭遇时间以及洪峰重现期等方面,重点分析了梧州站干支流洪水遭遇规律。研究表明:梧州15场洪水中红水河、柳江、郁江及桂江的日平均流量平均比重分别为32.31%、40.57%、13.19%及9.13%;其中西江干流洪水发生时间集中在6～8月,柳江洪水发生时间集中在6～7月,桂江洪水发生时间集中在5～7月,郁江洪水发生时间集中在7～9月;西江上游红水河与柳江洪水遭遇频繁,而郁江、桂江遭遇洪水量级较小,其中全流域洪水、红水河—柳江—桂江洪水、柳江—郁江—桂江洪水三种遭遇类型所构成的梧州大洪水重现期依次约为100年、50年、20年一遇,揭示了西江干支流洪水遭遇后致使梧州站洪水重现期显著增大。研究结果可为西江流域防洪减灾提供水文分析参考。     

Fe–Al–organic Colloids Control of Trace Elements in Peat Soil Solutions: Results of Ultrafiltration and Dialysis

Size fractionation of ~40 major and trace elements (TE) in peat soil solutions from the Tverskaya region (Russia) has been studied using frontal filtration and ultrafiltration through a progressively decreasing pore size (5, 2.5, 0.22 μm, 100, 10, 5, and 1 kD) and in situ dialysis through 6–8 and 1 kD membranes with subsequent analysis by ICP-MS. In (ultra) filter-passed permeates and dialysates of soil solutions, Fe, Al, and organic carbon (OC) are well correlated, indicating the presence of mixed organo-mineral colloids. All major anions and silica are present in “dissolved” forms passed through 1 kD membrane. According to their behavior during filtration and dialysis and association with mineral or organic components, three groups of elements can be distinguished: (i) species that are weakly affected by size separation operations and largely (>50–80%) present in the form of dissolved inorganic species (Ca, Mg, Li, Na, K, Sr, Ba, Rb, Cs, As, Mn) with some proportion of small (1–10 kD) organic complexes (Ca, Mg, Sr, Ba), (ii) biologically essential elements (Co, Ni, Zn, Cu, Cd) mainly present in the fraction smaller than 1 kD and known to form strong organic complexes with fulvic acids, and, (iii) elements strongly associated with aluminum, iron and OC in all ultrafiltrates and dialysates with 30–50% being concentrated in large (>10 kD) colloids (Ga, Y, REEs, Pb, Cd, V, Nb, Sn, Ti, Zr, Hf, Th, U). For most trace metals, the proportion in the colloidal fraction correlates with their first hydrolysis constant. This implies a strong control of negatively charged oxygen donors present in inorganic/organic colloids on TE distribution between aqueous solution and colloid particles. It is suggested that these colloids are formed during plant uptake of Al, Fe, and TE from mineral matrix of deep soil horizons and their subsequent release in surface horizons after litter degradation and oxygenation on redox or acid/base fronts. Dissolved organic matter stabilizes Al/Fe colloids and thus enhances trace elements transport in soil solutions.     

Trace element fractionation and transport in boreal rivers and soil porewaters of permafrost-dominated basaltic terrain in Central Siberia

The chemical status of ∼40 major and trace elements (TE) and organic carbon (OC) in pristine boreal rivers draining the basaltic plateau of Central Siberia (Putorana) and interstitial solutions of permafrost soils was investigated. Water samples were filtered in the field through progressively decreasing pore size (5 μm → 0.22 μm → 0.025 μm → 10 kDa → 1 kDa) using cascade frontal filtration technique. Most rivers and soil porewaters exhibit 2-5 times higher than the world average concentration of dissolved (i.e., <0.22 μm) iron (0.03-0.4 mg/L), aluminum (0.03-0.4 mg/L), OC (10-20 mg/L) and various trace elements that are usually considered as immobile in weathering processes (Ti, Zr, Ga, Y, REEs). Ultrafiltration revealed strong relationships between concentration of TE and that of colloidal Fe and Al. According to their partition during filtration and association with colloids, two groups of elements can be distinguished: (i) those weakly dependent on ultrafiltration and that are likely to be present as truly dissolved inorganic species (Li, Na, K, Si, Mn, Mo, Rb, Cs, As, Sb) or, partially (20-30%) associated with small size Fe- and Al-colloids (Ca, Mg, Sr, Ba) and to small (<1-10 kDa) organic complexes (Co, Ni, Cu, Zn), and (ii) elements strongly associated with colloidal iron and aluminum in all ultrafiltrates largely present in 1-100 kDa fraction (Ga, Y, REEs, Pb, V, Cr, Ti, Ge, Zr, Th, U). TE concentrations and partition coefficients did not show any detectable variations between different colloidal fractions for soil porewaters, suprapermafrost flow and surface streams. TE concentration measurements in river suspended particles demonstrated significant contribution (i.e., ?30%) of conventionally dissolved (<0.22 μm) forms for usually “immobile” elements such as divalent transition metals, Cd, Pb, V, Sn, Y, REEs, Zr, Hf, Th. The Al-normalized accumulation coefficients of TE in vegetation litter compared to basalts achieve 10-100 for B, Mn, Zn, As, Sr, Sn, Sb, and the larch litter degradation is able to provide the major contribution to the annual dissolved flux of most trace elements. It is hypothesized that the decomposition of plant litter in the topsoil horizon leads to Fe(III)-, Al-organic colloids formation and serves as an important source of elements in downward percolating fluids.     

Control of organic and iron colloids on arsenic partition and transport in high arsenic groundwaters in the Hetao basin, Inner Mongolia

Due to the importance of colloids in regulating element transport and mobility in aquifers, As distribution in the colloidal fraction needs to be identified in high As groundwaters. Groundwater samples were filtered in the field through a progressively decreasing pore size (0.45 μm, 100, 30, 10, 5 kDa) using a filtration technique under a N₂ atmosphere. Major and trace elements and organic C (OC) were measured in (ultra)filtrates. The studied groundwater samples have typical physio-chemical characteristics of the basin waters. Declines in concentrations of alkali (Na, K), alkaline-earth (Mg, Ca, Sr, Ba) elements, Mo, Si and Se during ultrafiltration are smaller relative to other elements. Arsenic, Cu, Cr, U and V are generally about 30% lower in 5 kDa ultrafiltrates in comparison with 0.45 μm filtrates. Around 50% of Fe, OC and Al are bound to colloids with grain size between 5 kDa and 0.45 μm. Two types of colloids, including large-size Fe colloids and small-size organic colloids, have been identified. Results indicate that As would be more likely to be associated with small-size organic colloids than Fe colloids. SEM images and EDS analysis and synchrotron XRF analyses confirm the association of As with NOM with molecular weights of 5-10 kDa. The better correlation between As(V) and OC in the 5-10 kDa fraction indicates that the small-size organic colloids have a greater affinity for As(V) than As(III). Arsenic associated with organic complexes may not be immobilized by adsorption, and, therefore, easily transported in the aquifer. Thus, the presence of As-containing colloidal complexes in high As groundwaters must be considered in the modeling of As transport in the aquifers.     

Geochemistry of the Kola River, northwestern Russia

The Kola River in the northern part of the Kola Peninsula, northwestern Russia, flows into the Barents Sea via the Kola Bay. The river is a unique place for reproduction of salmon and an important source of drinking water for more than 500,000 people in Murmansk and the surrounding municipalities. To evaluate the environmental status of the Kola River water, sampling of the dissolved (<0.22 μm) and suspended (>0.22 μm) phases was performed at 12 sites along the Kola River and its tributaries during 2001 and 2002. Major (Ca, K, Mg, Na, S, Si, HCO₃ and Cl) and trace (Al, As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Sr, Ti, and Zn) elements, total and particulate organic C (TOC and POC), N and P were analysed. Comparison with the boreal pristine Kalix River, Northern Sweden, shows that, except for Na, Cl, Al, Cu and Ni, which exceed the concentrations in the Kalix River by as much as 2–3 times, the levels of other major and trace elements are close to or even below the levels in the Kalix River. However, the results also demonstrate that pollutants from the three major sources: (1) the Cu–Ni smelter in Monchegorsk, (2) the open-pit Fe mine and ore concentration plant in Olenegorsk, and (3) the Varlamov, the Medveziy and the Zemlanoy creeks, draining the area of the large agricultural enterprises in the lower part of the watershed, have a major influence on the water quality of the Kola River.     

Chemical weathering in the drainage basin of a tropical watershed (Nsimi-Zoetele site, Cameroon) : comparison between organic-poor and organic-rich waters

This study deals with the weathering processes operating at the scale of a small catchment (Nsimi-Zoetele, Cameroon) and is focused on the role of organic colloids on mineral weathering and transport of elements in natural waters. Samples of river, spring and groundwaters from Nsimi-Zoetele were filtered through membranes of decreasing pore size (0.22 μm, 0.025 μm, or: 300,000 Da, 5000 Da) to separate colloidal fractions from the truly dissolved one. Major and trace elements and dissolved organic carbon (DOC) were analysed in each fraction. Two kinds of waters can be distinguished in the catchment: clear and coloured waters. Clear waters exhibit low concentrations of major and trace elements and DOC. Elements are carried in these solutions in a true dissolved form except Al and rare earth elements (REEs). By contrast, the higher abundances of Al, Fe and trace elements in coloured waters are controlled by the colloidal fraction. Thermodynamic equilibrium calculations show that clear waters are in equilibrium with kaolinite and iron oxi-hydroxide which are major minerals in the weathered soil. For coloured waters, the aqueous speciation of Ca, Mg, Cu, Fe, Al, La and Th was calculated taking into account the complexes with humic acids. Speciation calculations for Cu, Fe, Al, La, Th show a strong complexation with humic acids, in good agreement with the results of the filtration experiments. By contrast, although filtration experiments show a strong control of major cations by organic matter (for example 75% for Ca), speciation calculations reveal that their complexes with humic ligands do not exceed a few percent of total dissolved elements. This discrepancy is explained as an artefact induced by the organic colloids and occurring during the filtration procedure. Finally, both filtration experiments and speciation calculations show that organic matter plays an important role in natural DOC-rich waters. Organic acids increase significantly the dissolution rates of silicates and oxi-hydroxides and thus the amounts of solutes and of complexed elements leaving the catchment.     

近50 a来新疆区域与天山典型流域极端洪水变化特征及其对气候变化的响应

以年极端洪水超标率来反映区域极端洪水, 分析了新疆区域极端洪水变化; 以年最大洪峰记录分析了天山山区主要河流极端洪水变化规律, 并用14站资料分析了天山山区气候变化特征, 讨论了天山主要河流极端洪水变化对区域气候变化的响应. 结果表明: 受气候变暖影响, 1957-2006年全疆极端洪水呈区域性加重趋势, 尤其南疆区域极端洪水明显加剧, 北疆区域也有加重趋势, 但相对较缓. 全疆及北疆、 南疆在20世纪90年代中期以来都处于洪水高发阶段. 近50 a来, 在新疆区域洪水呈加重趋势的变化背景下, 发源于天山南坡的托什干河和库玛拉克河年最大洪峰流量呈显著增加趋势, 发源于天山北坡的玛纳斯河与乌鲁木齐河年最大洪峰流量虽有增加, 但是变化趋势较缓. 以年最大洪峰流量发生转折年为界, 天山典型流域托什干河、 库玛拉克河、 玛纳斯河和乌鲁木齐河在20世纪90年代(或80年代)以来与前期相比, 呈现出相似的变化特征: 年最大洪峰流量明显增大, 年际间变化更加剧烈, 洪水年更频繁. 以年最大洪峰流量发生转折年份为界, 玛纳斯河、 托什干河和乌鲁木齐河后期的年最大洪峰集中日期较前期推迟2~9 d, 库玛拉克河却提前5 d. 玛纳斯河、 乌鲁木齐河和库玛拉克河后期的集中度较前期增加0.8%~8.3%, 托什干河减小1.1%. 1961-2010年, 新疆天山山区气温明显上升, 升温率为0.34 ℃·(10a)^-1, 1997年以后明显增暖; 天山山区降水显著增加, 增加速率15.6 mm·(10a)^-1, 同时极端降水强度增大、 频数增多. 近50 a来天山主要河流极端洪水变化与区域增温以及天山山区极端降水事件增多等有密切关系.     

基于信息扩散理论的洪水风险评估模型的研究及应用--以阿克苏河流域新大河暴雨融雪型洪水为例

针对新疆一些河流实测洪水系列较短、传统的统计模型进行风险估计难以胜任的特点,引入了信息扩散理论的模糊数学方法,提出了洪水风险评估的实用模型,并以新疆阿克苏河流域新大河暴雨融雪型洪水为例,进行洪水风险估计,结果令人满意。     

Effects of colloids on metal transport in a river receiving acid mine drainage,upper Arkansas River,Colorado, U.S.A.

Inflows of metal-rich, acidic water that drain from mine dumps and tailings piles in the Leadville, Colorado, area enter the non-acidic water in the upper Arkansas River. Hydrous iron oxides precipitate as colloids and move downstream in suspension, particularly downstream from California Gulch, which has been the major source of metal loads. The colloids influence the concentrations of metals dissolved in the water and the concentrations in bed sediments. To determine the role of colloids, samples of water, colloids, and fine-grained bed sediment were obtained at stream-gaging sites on the upper Arkansas River and at the mouths of major tributaries over a 250-km reach. Dissolved and colloidal metal concentrations in the water column were operationally defined using tangential-flow filtration through 0.001-pm membranes to separate the water and the colloids. Surface-extractable and total bed sediment metal concentrations were obtained on the <60-μm fraction of the bed sediment. The highest concentrations of metals in water, colloids, and bed sediments occurred just downstream from California Gulch. Iron dominated the colloid composition, but substantial concentrations of As, Cd, Cu, Mn, Pb, and Zn also occurred in the colloidal solids. The colloidal load decreased by one half in the first 50 km downstream from the mining inflows due to sedimentation of aggregated colloids to the streambed. Nevertheless, a substantial load of colloids was transported through the entire study reach to Pueblo Reservoir. Dissolved metals were dominated by Mn and Zn, and their concentrations remained relatively high throughout the 250-km reach. The composition of extractable and total metals in bed sediment for several kilometers downstream from California Gulch is similar to the composition of the colloids that settle to the bed. Substantial concentrations of Mn and Zn were extractable, which is consistent with sediment-water chemical reaction. Concentrations of Cd, Pb, and Zn in bed sediment clearly result from the influence of mining near Leadville. Concentrations of Fe and Cu in bed sediments are nearly equal to concentrations in colloids for about 10 km downstream from California Gulch. Farther downstream, concentrations of Fe and Cu in tributary sediments mask the signal of mining inflows. These results indicate that colloids indeed influence the occurrence and transport of metals in rivers affected by mining.