Assessment of heavy metal contents in bed sediments of a mineralized catchment of the Agno River, Benguet, Philippines

Several former and existing gold and copper mines of the Benguet Province in northern Philippines are situated in the Baloy catchment. Rivers and tributaries drain an area of approximately 89 square kilometers before joining the main Agno River which drai…     

Mercury in river sediments, floodplains and plants growing thereon in the drainage area of the Idrija mine, Slovenia

Half a millennium mercury production at Idrija is reflected in increased mercury contents in all environmental segments. The bulk of roasting residues from the middle of the 19th century to 1977 was discharged directly into the Idrijca River, and the material was carried at high waters to the Soca River and farther into the Adriatic Sea. It has been estimated that 45500 tons of mercury were emitted into the environment during the operating period of the mine, which ceased production in 1994. In the lower reaches of the Idrijca the riverine deposits with high mercury contents have been, and will be in the future a source of mercury polluted sediment. Stream sediments were monitored at the same locations along the Idrijca and Soca rivers （70 kin） every 5 years since 1991 （1991-2005）. Grain size distribution was determined by dry sieving and fractions for geochemical analysis were prepared （〈0.04 and 〈0.125 mm）. Soils on river terraces were sampled at 5 localities in the lower course of Idrijca. At two locations of the terrace profiles the samples of averaged meadow forage and plantain （Plantago lanceolata） were collected within a 50-meters radius. We found that there was no decrease in mercury concentration in active river sediments during the last 20 years. Upstream from the Idrija Town the mercury concentrations in active river sediments vary from 1 to 10 mg/kg （average 3.3 mg/kg）. From Idrija to Spodnja Idrija the mercury concentrations increase extremely and vary greatly （32-4,121 mg/kg, the average is 734 mg/kg）. From Spodnja ldrija to the Idrijca-Soca confluence is the average 218 mg/kg, and 57 mg/kg downstream in the Soca River sediments.     

Rare-earth element geochemistry as a tracer for clarifying the provenance of the stream sediments in Namhan River, Korea

In the last forty years, the rare-earth elements （REEs） have been used as a powerful tool for solving various geological and geochemical problems due to their unique and chemically coherent behavior. The river sediments are produced by weathering, transportation and deposition. Nesbitt suggested that the rare-earth elements had been mobilized and fractionated during supracrustal alteration of the Torrongo granite, southeastern Australia. Nevertheless, recently, our replicate estimation for REE patterns in sediments revealed that there is nearly no variation in REE patterns. This suggests that invariability of REE patterns in weathering and solidification can be used as a tracer for constraining the provenance of stream sediments. In order to trace the pathway of the river sediments geochemically, based on the REE geochemistry from the river sediments and rocks, we have monitored the REE abundance of stream sediments at branch rivers of the Namhan River in South Korea for three years. The branches studied are Bokhacheon, Shinduncheon and Yanghwacheon. The sediments were divided into coarse （〉300 μm） and fine fractions （〈300 μm）. As a result, we could observe that major element compositions were similar to each other regardless of particle size and sampling date. This suggests that it is difficult to deduce a geochemical difference between river sediments based on major element composition and particle size. The geochemical characteristics of surrounding soils were similar to those of fine river sediments. And the chondrite-normalized REE patterns of most of the fine and coarse sediments in combination with grain sizes and drainage area showed very close relationship with the surrounding rocks. However, some sites showed that there were large variations in REE patterns including total REE abundance and Eu anomaly due to feldspars. This variation trend of REE patterns suggests that changes might have happened in sediment supply for the drainage system in the study area due to floods or large-scale construction.     

Combining forms of heavy metal elements in Dianshan Lake sediments and their spatial and temporal variations

Dianshan Lake is one of the important water supply sources for Shanghai City. The contents of heavy metals in the sediments are obviously higher than those in the overlying water body. The contents of Pb in the sediments vary seasonally; with increasing depth, the contents of Cd, Pb, Cu, Cr and Fe show no variation generally, but Mn varies in the peak pattern. Cd, Pb, Cu, Cr and Fe in the sediments are present predominantly in sludge phase, but iron and manganese oxide form of Pb and organic matter-sulfide form of Cu are their respective preferential combining forms. Manganese is present largely in exchangeable form, iron-manganese oxide combined form and sludge form. The contents of the various forms of Cd, Pb, Cu, Cr and Fe tend to vary with changing season and depth. The contents of exchangeable forms of Fe and Mn vary with depth in the peak-like pattern.     

Controls on the δ13CDIC and alkalinity budget of a flashy subtropical stream (Manoa River,Hawaii)

Hawaiian streams are flashy in nature because watersheds are small and steep and receive intense and unevenly distributed rainfall. As a result, stream chemistry is characterized by considerable spatiotemporal variability. To examine how rainfall and streamflow affect the solute content of the Manoa River in Hawaii, time-series geochemical data collected during 17 sampling campaigns in spring-fall of 2010 were evaluated in a coupled δ¹³C_DIC/major ion inversion model. Spatially, the stream is characterized by a distinct shift from a low HCO₃ (43 mg/L), low pCO₂ (3760 ppmv) and heavy δ¹³C_DIC (−6.5‰) fingerprint in the upper reaches to a high HCO₃ (91 mg/L), high pCO₂ (8961 ppmv) and light δ¹³C_DIC (−11.7‰) signature in the lowlands. These trends are attributed to (1) progressive weathering of exposed aluminosilicates, and (2) downstream enrichment in CO₂ from organic matter decay in the soil zone. Solute (i.e., nitrate) yields from nitric acid weathering are generally low (<1% of TDS), even in the developed lowlands, where runoff of nitrate-enriched urban effluent has historically been documented. Data furthermore indicate a significant positive correlation between δ¹³C_DIC and rainfall rates in the mid-stream section of the river which is consistent with an atmospheric CO₂ dilution effect during high rainfall events. This dilution effect needs to be accounted for to reliably describe the role of volcanic island river systems in global assessments of silicate weathering and CO₂ degassing.     

Heavy-metal enrichment in surficial sediments in the Oder River discharge area: source or sink for heavy metals?

The Oder river drains a highly polluted industrial area and enters the Baltic Sea through a system of shallow lagoons. Surficial sediments in the discharge area of the Oder are highly enriched in heavy metals compared to their preindustrial background levels. Pore-water studies in short sediment cores reveal anoxic environments over the entire sediment column, except for a suboxic layer in the uppermost 5 to 20 mm of the sediment where Mn- and Fe-oxyhydroxides are reduced by organic matter. Heavy metals (such as Cu, Zn and Pb) are mobilized within the suboxic zones in the inner lagoon (represented by the Oder Lagoon) and in the open Baltic (represented by the Arkona Basin). The Achterwasser, located between the Oder Lagoon and the Arkona Basin, is directly affected by sea-level fluctuations in the Baltic. Pore-water studies indicate that, in contrast to the situation in the Oder Lagoon and Arkona Basin, surficial sediments of the Achterwasser represent a sink for heavy metals. This is associated with the high rate of Fe-sulphide formation occurring there, at least seasonally during salt-water inflow.     

Distribution and speciation of mercury in soil in the area of an ancient mercury ore roasting site,Frbejžene trate (Idrija area,Slovenia)

In the initial period of mining activities in the Idrija basin (the16^th and the first half of the17^th centuries), Hg ore processing was performed at various small-scale roasting sites in the woods surrounding Idrija, by roasting ore in earthen vessels. The recovery rate of this method was very low; about half of Hg was lost, causing soil contamination and considerable amounts of waste material that could potentially leach Hg into the surrounding environment. The main aims of present geochemical study were to determine the contents, vertical distribution and speciation of Hg in soils at the roasting site at Frbej?ene trate in order to verify the extreme pollution of ancient Hg ore roasting sites in the Idrija area and to establish their significance in the wider spatial contamination of soils and aquatic systems. Soil sampling was performed at the area of the former roasting site. The organic matter-rich surface soil layer (SOM) and underlying mineral soil were sampled at 63 sampling locations. Mercury speciation was performed using Hg thermo-desorption-AAS to distinguish cinnabar from potentially bioavailable forms. The results indicate extremely high Hg concentrations with a maximum of 37,000 mg/kg in SOM and 19,900 mg/kg in mineral soil. The established Hg median in soil was 370 mg/kg and in SOM 96.3 mg/kg. Spatial distributions of Hg in SOM and soil showed very high Hg contents in the central area and decreased rapidly with distance. The results of Hg thermo-desorption measurements indicated the presence of cinnabar (HgS) and Hg bound to organic or mineral soil matter. A significant portion (35–40%) of Hg in the investigated soil and SOM samples was comprised of non-cinnabar compounds, which are potentially bioavailable. It has been shown that soils contain high amounts of potentially transformable non-cinnabar Hg, which is available for surface leaching and runoff into the surrounding environment. Therefore, contaminated soils and roasted residues at the studied area are important for persistent Hg release into the aquatic ecosystem.     

Contamination and bioavailability of heavy metals in sediments from the Yangtze River Delta Region

The Yangtze River Delta Region is one of the most important economic development areas in China. In the process of its industrialization and urbanization, a great deal of wastewater is poured into rivers, lakes and coasts. Researches on contamination and bioavailability of heavy metals can help us to assess the ecological risks in the aquatic environment of the Yangtze River Delta. The samples were collected from three environmental compartments including the Yangtze River, Taihu Lake, and the south coast of Jiangsu. The concentrations of heavy metals were determined by ICP-MS. Metal speciation was determined by the sequential extraction procedure modified based on Tessier＇s scheme. Among the seven elements of Cu, Pb, Zn, Cr, Cd, Co, Ni detected, the contents of Cr, Zn did not vary significantly, while Cd and Pb varied significantly. Compared to the background values （loess in the basement）, all metals detected except Co, Cr exceeded the background level. Cd had the greatest exceeding values, reaching 2 to 7 times. Ni and Pb were followed. The contents of Zn were comparatively high in lake sediments, especially in the lake bays. Ni was enriched in fiver sediments and Cu was highest in sediments from the Yangtze River estuary. Cd and Pb were concentrated in the coastal sediments. Comparatively, in space, Cr was associated with the carbonate fractions in the bay of lake. Cu-bound Fe-Mn oxides and Ni in residual form were highest in the open lake. In the river environment, Fe/Mn oxide-bound Pb, exchangeable Cd were the highest fractions. In the estuary environment, Pb and Zn bound carbonates, Cd-bound Fe-Mn oxides are the largest fractions. Cd in the exchangeable fraction, Cu-bound Fe-Mn oxides had the larger proportions in the coast. In general, the bioavailability of Cu and Cd were high in lake environment, the available Pb, Cd were remarked in river environment, and Pb and Zn were easily assimilated by creatures in estuary.     

New results of OSL dating of Quaternary sediments in the Upper Katun’ valley (Gorny Altai) and adjacent area

Several sections have been studied to understand the distribution and interrelation of basic genetic types of Quaternary deposits in the Uimon basin and adjacent area. The OSL date of 101 ± 10 ka from the glaciolacustrine terrace on the northeastern rim of the basin corresponds to the cool substage of MIS 5. The glaciolacustrine sediments of the northern rim are covered with widespread diamictic flows of the outburst draining of the ice-dammed lake. The diamicts are overlain by a subaerial complex of loesses and three fossil soils. From the OSL loess dates in the range of 43 to 49 ka we infer that the complex formed from the early MIS 3 through the Holocene. This is also supported by radiocarbon dates from alluvial deposits incised into the glaciolacustrine terrace and into megaflood sediments of the final draining of the last paleolake. The OSL dates in the range of 77 to 89 ka from alluvial sediments indicate that postglacial downcutting of the present-day Katun’ valley probably started just after MIS 5. The discrepancy between the beryllium dates from dropstones and Holocene TL-dates of the Katun’ valley floods ranging from 23 to 6 ka can be explained if the younger floods are related to the draining of moraine- and rock slide dammed rather than ice-dammed lakes. The younger floods, though being less voluminous than the glacial megafloods, were capable of producing giant ripple marks.     

Grain size and geochemical partitioning of heavy metals in sediments of the Damodar River – a tributary of the lower Ganga, India

 The distribution of Si, Al, Fe, Mn, Cu, Zn, Ni and Cr in different grain-size fractions and geochemical association of Fe, Mn, Cu and Zn with <63-μm size fraction of bed sediments of Damodar River has been studied. In general, concentrations of heavy metals tend to increase as the size fractions get finer. However at two sites, near mining areas, the coarser particles show similar or even higher heavy metal concentrations than finer ones. The higher residence time and/or presence of coarser particles from mining wastes are possibly responsible for higher metal content in the coarser size fractions. The chemical fractionation study shows that lithogenic is the major chemical phase for heavy metals. Fe and Mn are the major elements of the lithogenic lattice, constituting 34–63% and 22–59%, respectively, of total concentrations. Fe-Mn oxide and organic bound fractions are significant phases in the non-lithogenic fraction. The carbonate fraction is less significant for heavy metal scavenging in the present environment and shows the following order of abundance Zn>Cu>Mn>Fe. The exchangeable fraction of the Damodar sediments contains very low amounts of heavy metals suggesting poor bioavailability of metals. Received: 18 August 1998 · Accepted: 1 December 1998     

Spatial and temporal variations of physicochemical and heavy metal pollution in Ramganga River—a tributary of River Ganges,India

The River Ganges being the most sacred river and lifeline to millions of Indians in serving their water requirements is facing excessive threat of pollution. Under various river management and conservation strategies for its protection, the assessment of water quality of its main tributary Ramganga River is lacking. This study focuses on assessment of physicochemical and heavy metal pollution of the Ramganga River by application of multivariate statistical techniques. Sampling of Ramganga River at sixteen sampling sites was carried out in three seasons (summer, monsoon and winter) of 2014. The collected water samples were analyzed for physicochemical parameters and heavy metals. Results from cluster analysis (CA) of the data divided the whole stretch of the river into three clusters as elevation from 1304 to 259 m as less polluted, from 207 to 154 m as moderately polluted and from elevation 154 to 139 m as high-polluted stretches with anthropogenic as main sources of pollution in high-polluted stretch. Principal component analysis of the seasonal dataset resulted in three significant principal components (PC) in each season explaining 72–8% of total variance with strong loadings (>0.75) of PC1 on fluoride (F^?), chloride (Cl^?), sodium (Na⁺), calcium (Ca²⁺), magnesium (Mg²⁺), bicarbonate (HCO₃ ^?), total dissolved solids and electrical conductivity. Temporal variation by one-way ANOVA (Analysis of Variance) showed significant seasonal variation was in the pH, chemical oxygen demand, biochemical oxygen demand, turbidity, HCO₃ ^?, F^?, Zn, cadmium (Cd) and Mn (p < 0.05). Turbidity showed approximately a twofold increase in monsoon season due to rainfall in the catchment area and subsequent flow of runoff into the river. Concentration of HCO₃ ^?, F^? and pH also showed similar increase in monsoon. The concentration of Zn, Cd and Mn showed an increasing trend in summers compared to monsoon and winter season due to dilution effect in the monsoon season and its lasting effect in winters.     

Silicon and sediment transport of the Changjiang River (Yangtze River): could the Three Gorges Reservoir be a filter?

Water samples were collected from the Changjiang River (Yangtze River) in May 2005, after the impoundment of the Three Gorges Reservoir (TGR), to examine the influence of the TGR and large lakes on material delivery to the estuary of the Changjiang River. The concentrations of suspended particle material (SPM), dissolved silica (DSi) and biogenic silica (BSi) in the main stream were analyzed. The concentrations of DSi and BSi in the main channel of the Changjiang varied between 73 and 100 and 1.1–15 μmol/l, with a distance weighted average of 81 and 8.0 μmol/l, respectively. A calculation shows that live diatom comprises only an average value of 5.2 % of the BSi in the Changjiang River, and most of BSi may come from drainage basin. The concentrations of BSi and the ratios of BSi/SPM were relatively low in the Changjiang River compared to other rivers throughout the world, but the BSi carried in suspension by the Changjiang River was an important component of the rivers silicon load (i.e. ~13 %). SPM, DSi and BSi concentrations as observed in the Changjiang River tend to decrease from the upper sections of the river to the Three Gorges Dam (TGD), reflecting sedimentation associated with BSi trapping and DSi retention in the TGR in the normal-water period. SPM and BSi retention are more strongly influenced by the TGD compared to DSi. About 98 % of SPM, 72 % of BSi and 16 % of DSi were retained within the TGR in May 2005. The fluxes variations of DSi, BSi and SPM suggested that the large lakes and dams had a coupled effect on the transportation of DSi, BSi and SPM in the normal-water period. Such a change in silicon (DSi and BSi) balances of the Changjiang River will affect the ecological environment of the Changjiang estuary and its adjacent sea to some extent.     

Distribution of uranium and thorium in Irtysh River and the upriver wastewater from a rare metal mine impact on it

Uranium and Th are important radioactive elements. Most studies were focused on their environmental impact from uranium deposits and mining sites. But other sorts of mines such as rare metals mines are associated highly with uranium and thorium, too. In China, the Irtysh River is the only river that runs into the Arctic Ocean. The famous Koktokay rare metal pegmatite deposit is located in the headwater region of this river and has been exploited for several decades. The waste ore piled along the riverside as long as several kilometers. The wastewater flom the concentrating plant is discharged into the river directly. In addition, uranium and thorium can be leached from the waste ore into the river in the weathering process. So it is necessary to study the uranium and thorium distribution in the branch and trunk streams of the Irtysh River and the wastewater from the mining site impact on it. In this study, the contents of uranium and thorium in water samples from the Irtysh River and rare metal mine wastewater have been detected directly with ICP-MS. Uranium and thorium distribution and geochemical behaviors in the Irtysh River basin have been studied. The environmental uranium and thorium pollution status in the Irtysh River and wastewater from a rare metal mine impact on it have also been evaluated. The study shows that uranium and thorium contents in wastewater from a rare metal mine are as high as 78.311 μg/L and 0.627 μg/L, respectively, so we should also pay attention to the radioactive pollution from the rare metal mine. The average contents of U and Th in the branch streams of the Irtysh River are 0.572 μg/L and 0.015 μg/L, respectively. At the mean time, in the trunk of the Irtysh River, average thorium content is 0.019 μg/L while U is up to 2.234 μg/L, much higher than the average content （0.0309 μg/L） of the world rivers. From upstream to downstream in the trunk of the Irtysh River, thorium content declines gradually due to dilution by other branches and deposition itself.     

Net Ecosystem Metabolism and Nonconservative Fluxes of Organic Matter in a Tropical Mangrove Estuary, Piauí River (NE of Brazil)

Net ecosystem metabolism (NEM) was measured in the Piauí River estuary, NE Brazil. A mass balance of C, N, and P was used to infer its sources and sinks. Dissolved inorganic carbon (DIC) concentrations and fluxes were measured over a year along this mangrove dominated estuary. DIC concentrations were high in all estuarine sections, particularly at the fluvial end member at the beginning of the rainy season. Carbon dioxide concentrations in the entire estuary were supersaturated throughout the year and highest in the upper estuarine compartment and freshwater, particularly at the rainy season, due to washout effects of carbonaceous soils and different organic anthropogenic effluents. The estuary served as a source of DIC to the atmosphere with an estimated flux of 13 mol CO₂ m^?2 year^?1. Input from the river was 46 mol CO₂ m^?2 year^?1. The metabolism of the system was heterotrophic, but short periods of autotrophy occurred in the lower more marine portions of the estuary. The pelagic system was more or less balanced between auto- and heterotrophy, whereas the benthic and intertidal mangrove region was heterotrophic. Estimated annual NEM yielded a total DIC production in the order of 18 mol CO₂ m^?2 year^?1. The anthropogenic inputs of particulate C, N, and P, dissolved inorganic P (DIP), and DIC were significant. The fluvial loading of particulate organic carbon and dissolved inorganic nitrogen (DIN) was largely retained in two flow regulation and hydroelectric reservoirs, promoting a reduction of C:N and C:P particulate ratios in the estuary. The net nonconservative fluxes obtained by a mass balance approach revealed that the estuary acts as a source of DIP, DIN, and DIC, the latter one being almost equivalent to the losses to the atmosphere. Mangrove forests and tidal mudflats were responsible for most of NEM rates and are the main sites of organic decomposition to sustain net heterotrophy. The main sources for this organic matter are the fluvial and anthropogenic inputs. The mangrove areas are the highest estuarine sources of DIP, DIC, and DIN.     

Estimating contributions of sources of soil CO2 at the shallower layer in a Japanese larch forest area

Soils contain about twice the amount of carbon presented in the atmosphere, so a small change in the soil carbon will influence atmospheric chemistry and heat balance. The soil carbon ultimately exchanged with the atmospheric CO2 as soil CO2, which mainly exists at the depth of 0-20 cm. The transport of soil CO2 is affected by the sources of soil CO2. Thus, separation of the contributions of sources of soil CO2 is a fundamental need to understand and predict implications of environmental change on soil carbon cycling and sequestration. It is a complicated task, so that a number of different methodological approaches such as component integration, root removal, and gap analyses have been developed. However, these methods could not avoid changing soil characteristics such as air-filled porosity, soil temperature and soil water contents. Consequently, fractional contributions of respiration of living root and decomposition of soil organic matter to the total soil CO2 cannot be estimated correctly. In this study, based on mass balance theory of both concentrations and δ^13C of soil CO2, a trenching method with a stable-isotope technique was used to determine both soil CO2 sources at the depth of 3-13 cm in a Japanese larch forest area during 30 May to 7 October 2005 and fractional contributions of these sources. Experimental results showed that the amount of atmospheric CO2 invaded the soil air was not significantly variable while its percent rate in the total soil CO2 had significantly temporal variations with the lower values between 5 August and 1 September. The litter-layer decomposition was very small. The soil CO2 derived from the respiration of living root and the decomposition of soil organic matter showed significantly temporal variations with increase from 30 May to 5 Aug. and decrease from 1 September to 7 October, 2005; and it accounted for 82%-98% of the total soil CO2 in which the respiration of living root was in the range from 32% to 62%.     

Estimating contributions of sources of soil CO_2 at the shallower layer in a Japanese larch forest area

Soils contain about twice the amount of carbon presented in the atmosphere, so a small change in the soil carbon will influence atmospheric chemistry and heat balance. The soil carbon ultimately exchanged with the atmospheric CO2 as soil CO2, which mainly…     

Evaluation of trace element concentration (acid leachable) in sediments from River Pánuco and its adjacent lagoon areas, NE México

A set of forty-one surface sediment samples were collected in River Pánuco and its adjoining lagoon areas in NE Mexico to identify the enrichment pattern of trace elements. The samples were analyzed for sediment texture, carbonates, organic carbon and acid leachable trace elements (ALTEs) using autoclave method [Fe, Mn, Cr, Cu, Ni, Co, Pb, Zn, Cd, V, Be, Ba, Sr, As]. Geochemical results of Fe, Cr, Ni, Co, V and Sr in zone 1 indicate that erosion in the upland region (Sierra Madre Oriental Mountains) is very high. The above feature is supported by the supremacy of finer sediments (82.12 %), carbonates (44.67 %) and organic carbon (10.74 %), which are brought down from the drainage basin. The overall average concentration of ALTEs Mn (607 μg g^?1), Cu (28.29 μg g^?1), Ni (16.56 μg g^?1), Pb (46.11 μg g^?1), Cd (1.81 μg g^?1) and Zn (92.18 μg g^?1) indicates higher values than the lowest effect level (LEL) and effects range low (ERL) of environmental indicators. The results suggest that they are due to the increase in oil refineries, metal based industries, shipping activities and the effluent input which could enter the biological cycle and might create human health problems.