Chemodynamics of trace metal fractions in surface sediments of the Pandoh Lake,Lesser Himalaya,India

The seasonal variation in the trace metals’ concentrations (Cd, Co, Cu, Fe, Mn, Ni, Pb, and Zn) were investigated in surface sediments of the Pandoh Lake. The horizontal distribution of TC, TN, and TP reflects spatial and temporal differences in sedimentary organic production. The chemical sequential extraction of heavy metals was carried out by seven-step fractionation scheme (Leleyter and Probst in Int J Environ Chem 73:109–128, 1999). The significant concentrations of Ni and Cd were associated with “water soluble (Eua)” fraction in the monsoon and winter, respectively, while “exchangeable (Exch)” and “carbonate-bound (Carb)” fractions for Ni and Cd were abundant in winter and summer. The Cd, Cu, and Pb associated with “Exch” fraction in the summer season support their availability on exchange sites due to oxidized nature of surface sediments. Enrichment of Co, Fe, Mn, and Zn in “AFeO” fraction showed poor bioavailability, while Cd, Cu, and Mn in the monsoon, Co in the winter and summer, and Zn in the winter season showed significant “organically bound (Org)” fraction. The ANOVA was significant for chemical fractions of trace elements except “Carb” fraction of Pb and Zn and “CFeO” fraction of Pb. Factor analysis revealed that the “Eua”, “Exch”, and “Carb” fractions together control the metal enrichment of “MnO”, “AFeO”, and “CFeO” fractions in the summer season.     

Phosphorus speciation and availability in intertidal sediments of the Yangtze Estuary,China

In order to better understand P cycling and bioavailability in the intertidal system of the Yangtze Estuary, both surface (0–5 cm) and core (30 cm long) sediments were collected and sequentially extracted to analyze the solid-phase reservoirs of sedimentary P: loosely sorbed P; Fe-bound P; authigenic P; detrital P; and organic P. The total sedimentary P in surface and core sediments ranged from 14.58–36.81 μmol g⁻¹ and 17.11–24.55 μmol g⁻¹, respectively, and was dominated by inorganic P. The average percentage of each fraction of P in surface sediments followed the sequence: detrital P (54.9%) > Fe-bound P (23.7%) > organic P (14.3%) > authigenic P (6.3%) > loosely sorbed P (0.8%), whereas in core sediments it followed the sequence: detrital P (61.7%) > Fe-bound P (17.0%) > authigenic P (13.1%) > organic P (7.5%) > loosely sorbed P (0.7%). Post-depositional reorganization of P was observed in both surface and core sediments, converting organic P and Fe-bound P to authigenic P. The accumulation rates and burial efficiencies of the total P in the intertidal area ranged from 118.70–904.98 μmol cm⁻² a⁻¹ and 80.29–88.11%, respectively. High burial efficiency of the total P is likely related to the high percentage of detrital P and the high sediment accumulation rate. In addition, the bioavailable P represented a significant proportion of the sedimentary P pool, which on average accounted for 37.4% and 25.1% of the total P in surface and core sediments, respectively. This result indicates that the tidal sediment is a potential internal source of P for this P-limiting estuarine ecosystem.     

Seasonal variation in temperature and salinity in the Gautami-Godavari estuary

Variation of temperature and salinity in the lower 22 km stretch of the Gautami-Godavari estuary are reported during four different seasons; hot-weather, south-west monsoon, post-monsoon and winter seasons. The seasonal variation in temperature is small, with a high of about 30°C during hot-weather season and a low of about 26°C during winter season. Unlike temperatures, the salinities in the estuary show large seasonal fluctuations. During south-west monsoon surface salinities were low (0 to 8‰) due to high fresh water run off into the estuary. During hot-weather season surface salinities of 25 to 30‰ were observed due to negligible fresh water run off.     

Biogeochemical redox cycling of arsenic in mine-impacted lake sediments and co-existing pore waters near Giant Mine,Yellowknife Bay,Canada

Lacustrine sediments, submerged tailings, and their pore waters have been collected at several sites in Yellowknife Bay, Great Slave Lake, Canada, in order to investigate the biogeochemical controls on the remobilization of As from mining-impacted materials under different depositional conditions. Radiometric dating confirms that a mid-core enrichment of Pb, Zn, Cu and Sb corresponds to the opening of a large Au mine 60 a ago. This was evident even in a relatively remote site. Arsenic was enriched at mid-core, coincident with mining activity, but clearly exhibited post-depositional mobility, migrating upwards towards the sediment water interface (SWI) as well as down-core. Deep-water (15 m) Yellowknife Bay sediments that contain buried mine waste are suboxic, relatively organic-rich and abundant in microbes with As in pore waters and sediments reaching 585 μg/L and 1310 mg/kg, respectively. Late summer pore waters show equal proportions of As(III) and As(V) (16–415 μg/L) whereas late winter pore waters are dominated by As(III) (284–947 μg/L). This can be explained by As(III) desorption mechanisms associated with the conversion of FeS to FeS₂ and the reduction of As(V) to As(III) through the oxidation of dissolved sulfide, both microbially-mediated processes. Processes affecting As cycling involve the attenuating efficiency of the oxic zone at the SWI, sediment redox heterogeneity and the reductive dissolution of Fe(hydr)oxides by labile organic matter, temporarily and spatially variable.     

Winter and summer monsoonal evolution in northeastern Qinghai-Tibetan Plateau during the Holocene period

Climate change especially moisture condition in the northeastern Qinghai-Tibetan in China are mainly controlled by the strength and variability of Asian winter and summer monsoon. In this paper, we presented the climate record and related winter and summer monsoonal history in Gonghe Basin, northeastern Qinghai-Tibetan Plateau, based on the geochemical indicators (geochemical elements content, i.e., Fe₂O₃, CaO, Zr and Sr content, and geochemical parameters, i.e., the chemical index of alteration (CIA), Zr/Rb, Rb/Sr, CaO/MgO, SiO₂/TiO₂ and SiO₂/(Al₂O₃ + Fe₂O₃) ratio) of the peat deposits and ¹⁴C and OSL technologies. The regional temperature and humidity gradually increased in 10.0–8.5 cal ka BP, accompanied by enhanced summer monsoonal strength and decreased winter monsoonal strength. But climate became cold and dry between 8.5 cal ka BP and 7.6 cal ka BP owing to the stronger winter monsoon. During the 7.6–3.8 cal ka BP, stronger summer monsoon and weaker winter monsoon led to an optimal warm and humid condition, although it had several cold phases. From 3.8 cal ka BP to 0.5 cal ka BP, the regional climate tended to be cold and dry, with increasing winter monsoonal strength and decreasing summer monsoonal strength. Thereafter, the relatively warm and humid climate appeared again, due to the stronger summer monsoon. That is to say, the regional climate conditions are mainly related to the winter and summer monsoonal changes. These changes are consistent with palaeoclimatic records (monsoonal model) from the region influenced by the Asian monsoon in eastern China. In addition, nine cold events were recorded: 8.5–7.8 cal ka BP, 6.1–5.6 cal ka BP, 5.2–4.8 cal ka BP, 4.7–4.3 cal ka BP, 4.1–4.0 cal ka BP, 3.8–3.4 cal ka BP, 3.0–2.3 cal ka BP, 1.4–1.3 cal ka BP, and 1.0–0.5 cal ka BP, which are coincident with cold fluctuations in the high and low latitudes of the Northern Hemisphere on a millennial scale, as recorded by lakes, peat sediments, and ice cores in the Qinghai-Tibetan Plateau. In conclusion, Holocene millennial-scale climatic changes in Gonghe Basin were controlled by the dual function of Asian monsoonal changes and global cold fluctuations.     

Meteorological impacts on the water quality in the Pajuluoma acid sulphate area,W. Finland

Water samples (n = 354) from a small catchment (7.4 km²) covered by acid sulphate soils (pH < 4) were collected during all seasons and all types of hydrological conditions in 1990–2001. The electric conductivity (EC) and pH, i.e. the key indicators of acid sulphate soil impact in the current setting, were determined. Representative daily runoff and precipitation data was available for the whole study period. The 10th and 90th percentiles for EC and pH were 29–140 mS/m and 3.8–4.6, respectively. While the water quality varied remarkably from year to year, and even within seasons, some regularity was found. The water quality was generally worst in late autumn (water temperature < 5 °C) and in spring. Of all seasons the variations were clearly smallest in spring, indicating that most representative samples can be obtained in this season. There were significant correlations between autumn, early winter and spring water quality within hydrological years. Thus acid and metal surges in spring are somewhat predictable. At base flow conditions (runoff about 1 L/s km² or less), the water quality was relatively good in all seasons. Above base flow conditions, the impact of acid sulphate soils tended to slightly increase with increasing runoff and precipitation, especially in early summer, but not in late summer. No significant signs of dilution during flood conditions (up to 100 L/s km²) were found and neither were there any correlations to rising or falling limbs. The severity of individual summer droughts, which in theory should increase the oxidation of S and acidity in the soils, had little or no impact on the water quality in subsequent autumn and spring. On the other hand, there was a remarkable long-term increase in EC and a corresponding decrease in pH (starting in 1995) after a suite of several very dry summers. After that the water quality did not improve even if the dry summers were followed by some wet summers. This indicates that the temporary pool of readily leachable acidity in the soils is fairly large. Moreover, it indicates that the potential shift towards more extreme global weather conditions (with more severe dry spells) may have significant impacts on the water quality in midwestern Finland, a region that is heavily affected by acidity and metals from acid sulphate soils.     

Spatial and temporal variability in maximum,minimum and mean air temperatures at Madhya Pradesh in central India

In the present study, an investigation has been made to study the spatial and temporal variability in the maximum, the minimum and the mean air temperatures at Madhya Pradesh (MP), in central India on monthly, annual and seasonal time scale from 1901 to 2002. Further, impact of urbanization and cloud cover on air temperature has been studied. The annual mean, maximum and minimum temperatures are increased by 0.60, 0.60 and 0.62 °C over the past 102 years, respectively. Seasonally, the warming is more pronounced during winter than summer. The temperature decreased during the less urbanized period (from 1901 to 1951) and increased during the more urbanized period (1961 to 2001). It is also found that the minimum temperature increased at higher rate (0.42 °C) followed by the mean (0.36 °C) and the maximum (0.32 °C) temperature during the more urbanized period. Furthermore, cloud cover is significantly negatively related with air temperature in monsoon season and as a whole of the year.     

Arsenic mobility in fluvial environment of the Ganga Plain,northern India

In the northern part of the Indian sub-continent, the Gomati River (a tributary of the Ganga River) was selected to study the dynamics of Arsenic (As) mobilization in fluvial environment of the Ganga Plain. It is a 900-km-long, groundwater-fed, low-gradient, alluvial river characterized by monsoon-controlled peaked discharge. Thirty-six water samples were collected from the river and its tributaries at low discharge during winter and summer seasons and were analysed by ICP-MS. Dissolved As and Fe concentrations were found in the range of 1.29–9.62 and 47.84–431.92 μg/L, respectively. Arsenic concentration in the Gomati River water has been detected higher than in its tributaries water and characteristically increases in downstream, attributed to the downstream increasing of Fe₂O₃ content, sedimentary organic carbon and silt-clay content in the river sediments. Significant correlation of determination (r ² = 0.68) was also observed between As and Fe concentrations in the river water. Arsenic concentrations in the river water are likely to follow the seasonal temperature variation and reach the level of World Health Organization’s permissible limit (10 μg/L) for drinking water in summer season. The Gomati River longitudinally develops reducing conditions after the monsoon season that mobilize As into the river water. First, dissolved As enters into pore-water of the river bed sediments by the reductive dissolution of Fe-oxides/hydroxides due to microbial degradation of sedimentary organic matter. Thereafter, it moves upward as well as down slope into the river water column. Anthropogenically induced biogeochemical processes and tropical climatic condition have been considered the responsible factors that favour the release of As in the fluvial environment of the Ganga Plain. The present study can be considered as an environmental alarm for future as groundwater resources of the Ganga–Brahmaputra Delta are seriously affecting the human–environment relationship at present.     

Formation,fate and leaching of chloroform in coniferous forest soils

Chloroform is a common groundwater pollutant but also a natural compound in forest ecosystems. Leaching of natural chloroform from forest soil to groundwater was followed by regular analysis of soil air and groundwater from multilevel wells at four different sites in Denmark for a period of up to 4 a. Significant seasonal variation in chloroform was observed in soil air 0.5 m below surface ranging at one site from 120 ppb by volume in summer to 20 ppb during winter. With depth, the seasonal variation diminished gradually, ranging from 30 ppb in summer to 20 ppb during winter, near the groundwater table. Chloroform in the shallowest groundwater ranged from 0.5–1.5 μg L⁻¹ at one site to 2–5 μg L⁻¹ at another site showing no clear correlation with season. Comparing changes in chloroform in soil air versus depth with on-site recorded meteorological data indicated that a clear relationship appears between rain events and leaching of chloroform. Chloroform in top soil air co-varied with CO₂ given a delay of 3–4 weeks providing evidence for its biological origin. This was confirmed during laboratory incubation experiments which further located the fermentation layer as the most chloroform producing soil horizon. Sorption of chloroform to soils, examined using ¹⁴C–CHCl₃, correlated with organic matter content, being high in the upper organic rich soils and low in the deeper more minerogenic soils. The marked decrease in chloroform in soil with depth may in part be due to microbial degradation which was shown to occur at all depths by laboratory tests using ¹⁴C–CHCl₃.     

Sediment pore-water interactions associated with arsenic and uranium transport from the North Cave Hills mining region,South Dakota,USA

The extent of historical U mining impacts is well documented for the North Cave Hills region of Harding County, South Dakota, USA. While previous studies reported watershed sediment and surface water As and U concentrations up to 90× established background concentrations, it was unclear whether or how localized changes in sediment redox behavior may influence contaminant remobilization. Five pore-water equilibration samplers (peepers) were spatially and temporally deployed within the study area to evaluate seasonal solid–liquid As and U distributions as a function of sediment depth. Pore-water and solid phase As and U concentrations, Fe speciation, Eh and pH were measured to ascertain specific geochemical conditions responsible for As and U remobilization and transport behavior. At a mine overburden sedimentation pond adjacent to the mine sites, high total aqueous As and U concentrations (4920 and 674 μg/L, respectively) were found within surface water during summer sampling; however pond dredging prior to autumn sampling resulted in significantly lower aqueous As and U concentrations (579 and 108 μg/L, respectively); however, both As and U still exceeded regional background concentrations (20 and 18 μg/L, respectively). At a wetlands-dominated deposition zone approximately 2 km downstream of the sedimentation pond, pore-water geochemical conditions varied seasonally. Summer conditions promoted reducing conditions in pore water, resulting in active release of As(III) to the water column. Autumn conditions promoted oxidizing conditions, decreasing pore-water As (As_pw) 5× and increasing U_pw 10×. Peak U pore-water concentrations (781 μg/L) were 3.5× greater than determined for the surface water (226 μg/L), and approximately 40× background concentrations. At the Bowman–Haley reservoir backwaters 45 km downstream from the mine sites, As and U pore-water concentrations increased significantly between the summer and autumn deployments, attributed to increased Fe reduction processes. Geochemical modeling suggests solid-phase Fe reduction promotes the liberation of pore-water As and U via suppressing the formation of thioarsenite. Intermittent hydrological processes facilitate As and U transport and deposition throughout the watershed, while biogeochemical-influenced redox changes cycle As and U between pore and surface water within localized environments.     

Behavior of metals (Cu,Zn and Cd) in the initial stage of water system contamination: Effect of pH and suspended particles

The fate of potentially harmful metals (PHM) after their entry into an unpolluted fresh water body depends on the physicochemical and biological parameters of the aquatic ecosystem. This paper considers the effect of pH and suspended particles (SP) on the behavior of Cu, Zn and Cd when they enter a fresh water reservoir. In a field experiment, four mesocosms were constructed in the Novosibirskoye Reservoir to allow systematic variation of SP concentration (15 or 250 mg/L) and pH (8.5 or 6.5). The initial concentrations of Cu, Zn and Cd in the mesocosms were 1000, 1000 and 200 μg/L, respectively. Natural bottom sediments were used to provide additional mineral SP, and water hyacinth was used as a floating plant species. Over 11 days, measurements were made of several indicators: residual metal concentration in solution ([PHM]_w); metal concentration in SP ([PHM]_s); primary productivity of the phytoplankton community; mass of settled SP; PHM concentration in settled SP; and PHM bioaccumulation by water hyacinth. The ratio [PHM]_w/[PHM]_s in the water varied in the order Cu < Zn < Cd and was higher at pH 6.5 than at pH 8.5. This observation reflects different PHM sorption (Cu > Zn > Cd) onto mineral SP and PHM biosorption by planktonic organisms. Phytoplankton acts as a renewable source of organic SP and plays an important role in metal removal from the water in the mesocosms. After 11 days the residual concentrations of Cu, Zn and Cd in the mesocosm without SP addition (initial SP concentration was 15 mg/L) were 272, 355 and 84 μg/L, respectively. The residual concentrations of Cu, Zn and Cd in mesocosms with SP addition were 57, 100 and 14 μg/L at pH 8.5 and 80, 172 and 20 μg/L at pH 6.5, respectively. Therefore, addition of SP resulted in faster and more complete removal of metals into the bottom sediments. Floating plants (water hyacinth) accumulated PHM (Cu > Zn > Cd) more effectively at pH 8.5 than at pH 6.5, and PHM concentrations in the roots were higher than in settling SP. The general trends of PHM removal from contaminated water via sedimentation and bioaccumulation are compared with changes of metal speciation in solution.     

Global distributions of Fe,Al, Cu,and Zn contained in Earth's derma layers

To improve the usefulness and accuracy of modeling Earth's anthrobiogeochemical metal cycles, global maps at approximately 1° × 1° are produced of the concentrations and masses of Fe, Al, Cu, and Zn contained in continental sediments and soils. The maps generated utilize inverse distance weighting (IDW) and cokriging to generate new estimates for geospatially weighted mean global concentrations for these metallic micronutrients. Sediment metal concentration maps are generated from IDW of sediment samples; global soil maps are produced via cokriging upon an underlying parent rock dataset composed of both surface bedrock and sediment samples. Derived are independent estimates for the global mean concentrations in continental sediments (Fe = 3.1 wt.%, Al = 6.1 wt.%, Cu = 45 μg/g, Zn = 86 μg/g) and soils (Fe = 2.5 wt.%, Al = 3.9 wt.%, Cu = 17 μg/g, Zn = 50 μg/g). While continental sediment concentrations for Cu are within the range of previous estimates, Zn concentrations are relatively higher, ~ 20 μg/g above previous estimates. Fe and Al are slightly depleted (~ 1 wt.%) in continental sediments relative to previous estimates, likely ascribable to sampling bias and error inherent in the comparative methodologies. Besides an estimated global mean, metal concentrations in soils are also broken down by FAO soil group. Metal masses in sediments and soils remain within 30% of previous, non-spatial estimates. These maps also illustrate the discernable spatial variability across the Earth's surface. Despite data gaps, maps of metal mass show regional patterns such as the high quantities of Al in the soils and biomass of the Amazonia and Congo regions. Concentrations of metals are relatively high in the anthrosols of China. Finally, this analysis highlights those areas for which generating and providing publically available geochemical data should be prioritized. For instance, gypsisols, lixisols, and nitisols have little to no analytical data available on metal contents. A sensitivity analysis suggests that the most poorly constrained soil metal concentrations occur in the thick, old tropical soils of central Africa and the anthrosols of eastern China.     

Total particulate and reactive gaseous mercury in ambient air on the eastern slope of the Mt. Gongga area,China

Total particulate mercury (TPM) and reactive gaseous mercury (RGM) concentrations in ambient air on the eastern slope of the Mt. Gongga area, Sichuan Province, Southwestern China were monitored from 25 May, 2005 to 29 April, 2006. Simultaneously, Hg concentrations in rain samples were measured from January to December, 2006. The average TPM and RGM concentrations in the study site were 30.7 and 6.2 pg m⁻³, which are comparable to values observed in remote areas in Northern America and Europe, but much lower than those reported in some urban areas in China. The mean seasonal RGM concentration was slightly higher in spring (8.0 pg m⁻³) while the minimum mean concentration was observed in winter (4.0 pg m⁻³). TPM concentrations ranged across two orders of magnitude from 5.2 to 135.7 pg m⁻³ and had a clear seasonal variation: winter (74.1 pg m⁻³), autumn (22.5 pg m⁻³), spring (15.3 pg m⁻³) and summer (10.8 pg m⁻³), listed in decreasing order. The annual wet deposition was 9.1 μg m⁻² and wet deposition in the rainy season (May–October) represented over 80% of the annual total. The temporal distribution of TPM and RGM suggested distinguishable dispersion characteristics of these Hg species on a regional scale. Elevated TPM concentration in winter was probably due to regional and local enhanced coal burning and low wet deposition velocity. The RGM distribution pattern is closely related to daily variation in UV radiation observed during the winter sampling period indicating that photo-oxidation processes and diurnal changes in meteorology play an important role in RGM generation.     

浙闽沿岸南部泥质沉积中心表层沉积物粒度特征及其季节性差异

通过对浙闽沿岸南部泥质沉积中心15个站位夏季和冬季表层沉积物的粒度分析和对比,探讨了表层沉积物粒度的分布特征、季节性差异及其影响因素。研究结果表明,各站样品以黏土质粉砂为主,各粒度参数差别较小,平均粒径和标准偏差呈显著的负相关,偏态和尖态呈弱负相关。粒级—标准偏差曲线上,在4.92～6.46和25.32～33.27 μm之间存在高峰值,在11.16～13.39 μm之间为低谷值。粒度分布具有季节性差异,冬季样品各粒度参数分布范围均高于夏季,平均粒径（值）总体上比夏季的要小,偏态和尖态等值线的梯度明显大于夏季的。在粒级—标准偏差曲线上,冬季样品的变化程度要显著高于夏季的。粒度分布的差异主要受物质来源和海洋动力环境的季节性变化影响。     

Arsenic and antimony contamination of waters,stream sediments and soils in the vicinity of abandoned antimony mines in the Western Carpathians,Slovakia

Environmental contamination with As and Sb caused by past mining activities at Sb mines is a significant problem in Slovakia. This study is focused on the environmental effects of the 5 abandoned Sb mines on water, stream sediment and soil since the mines are situated in the close vicinity of residential areas. Samples of mine wastes, various types of waters, stream sediments, soils, and leachates of the mine wastes, stream sediments and selected soils were analyzed for As and Sb to evaluate their geochemical dispersion from the mines. Mine wastes collected at the mine sites contained up to 5166 mg/kg As and 9861 mg/kg Sb. Arsenic in mine wastes was associated mostly with Fe oxides, whereas Sb was present frequently in the form of individual Sb, Sb(Fe) and Fe(Sb) oxides. Waters of different types such as groundwater, surface waters and mine waters, all contained elevated concentrations of As and Sb, reaching up to 2150 μg/L As and 9300 μg/L Sb, and had circum-neutral pH values because of the buffering capacity of abundant Ca- and Mg-carbonates. The concentrations of Sb in several household wells are a cause for concern, exceeding the Sb drinking water limit of 5 μg/L by as much as 25 times. Some attenuation of the As and Sb concentrations in mine and impoundment waters was expected because of the deposition of metalloids onto hydrous ferric oxides built up below adit entrances and impoundment discharges. These HFOs contained >20 wt.% As and 1.5 wt.% Sb. Stream sediments and soils have also been contaminated by As and Sb with the peak concentrations generally found near open adits and mine wastes. In addition to the discharged waters from open adits, the significant source of As and Sb contamination are waste-rock dumps and tailings impoundments. Leachates from mine wastes contained as much as 8400 μg/L As and 4060 μg/L Sb, suggesting that the mine wastes would have a great potential to contaminate the downstream environment. Moreover, the results of water leaching tests showed that Sb was released from the solids more efficiently than As under oxidizing conditions. This might partly explain the predominance of Sb over As in most water samples.     

Experimental study of cadmium interaction with periphytic biofilms

This study addresses the interaction of Cd with natural biofilms of periphytic diatoms grown during different seasons in metal-contaminated and metal-non-contaminated streams, along a tributary of the Lot River, France. Specifically, it aims to test whether the biofilms from contaminated sites have developed a protective mechanism due to high Cd exposure. Towards this goal, reversible adsorption experiments on untreated biofilms were performed in 0.01 M NaNO₃ with a pH ranging from 2 to 8, Cd concentration from 0.5 to 10,000 μg/L and exposure time from 1 to 24 h. Two types of experiments, pH-dependent adsorption edge and constant-pH “Langmuirian”-type isotherms were conducted. Results were adequately modeled using a Linear Programming Model. It was found that the adsorption capacities of natural biofilm consortia with respect to Cd do not depend on season and are not directly linked to the growth environment. The biofilms grown in non-contaminated (4.6 ppb Cd in solid) and contaminated (570 ppb Cd in solid) settings exhibit similar adsorption capacities in the Cd concentration range in solution of 100–10,000 μg/L but quite different capacities at low Cd concentration (0.5–100 μg/L); unexpectedly, the non-contaminated biofilm adsorbs approximately 10 times more Cd than the contaminated one. It is therefore possible that the strong low-abundant ligands (for example, phosphoryl or sulfhydryls) are already metal-saturated on surfaces of biofilm grown in the contaminated site whereas these sites are still available for metal adsorption in samples grown in non-contaminated sites.     

Sources and flux of trace elements in river water collected from the Lake Qinghai catchment,NE Tibetan Plateau

River waters play a significant role in supplying naturally- and anthropogenically-derived materials to Lake Qinghai, northeastern Tibetan Plateau. To define the sources and controlling processes for river water chemistry within the Lake Qinghai catchment, high precision ICP-MS trace element concentrations were measured in water samples collected from the Buha River weekly in 2007, and from other major rivers in the post-monsoon (late October 2006) and monsoon (late July 2007) seasons. The distributions of trace elements vary in time and space with distinct seasonal patterns. The primary flux in the Buha River is higher TDS and dissolved Al, B, Cr, Li, Mo, Rb, Sr and U during springtime than those during other seasons and is attributed to the inputs derived from both rock weathering and atmospheric processes. Among these elements, the fluxes of dissolved Cr, B and Rb are strongly influenced by eolian dust input. The fluxes of dissolved Li, Mo, Sr and U are also influenced by weathering processes, reflecting the sensitivity of chemical weathering to monsoon conditions. The anthropogenic sources appear to be the dominant contribution to potentially harmful metals (Ni, Cu, Co, Zn and Pb), with high fluxes at onset of the main discharge pulses due, at least partially, to a runoff washout effect. For other major rivers, except for Ba, concentrations of trace elements are higher in the monsoon than in the post-monsoon season. A total of 38.5 ± 3.1 tons of potentially harmful elements are transported into the lake annually, despite human activities within the catchment being limited. Nearly all river water samples contain dissolved trace elements below the World Health Organization guidelines for drinking water, with the exception of As and B in the Daotang River water samples collected in late July probably mobilized from underlying lacustrine sediments.     

Evidence of microbially mediated arsenic mobilization from sediments of the Aquia aquifer, Maryland, USA

Sediments from the Aquia aquifer in coastal Maryland were collected as part of a larger study of As in the Aquia groundwater flow system where As concentration are reported to reach levels as high as 1072 nmol kg⁻¹, (i.e., ∼80 μg/L). To test whether As release is microbially mediated by reductive dissolution of Fe(III) oxides/oxyhydroxides within the aquifer sediments, the Aquia aquifer sediment samples were employed in a series of microcosm experiments. The microcosm experiments consisted of sterilized serum bottles prepared with aquifer sediments and sterilized (i.e., autoclaved), artificial groundwater using four experimental conditions and one control condition. The four experimental conditions included the following scenarios: (1) aerobic; (2) anaerobic; (3) anaerobic + acetate; and (4) anaerobic + acetate + AQDS (anthraquinone-2,6-disulfonic acid). AQDS acts as an electron shuttle. The control condition contained sterilized aquifer sediments kept under anaerobic conditions with an addition of AQDS. Over the course of the 27 day microcosm experiments, dissolved As in the unamended (aerobic and anaerobic) microcosms remained constant at around ∼28 nmol kg⁻¹ (2 μg/L). With the addition of acetate, the amount of As released to the solution approximately doubled reaching ∼51 nmol kg⁻¹ (3.8 μg/L). For microcosm experiments amended with acetate and AQDS, the dissolved As concentrations exceeded 75 nmol kg⁻¹ (5.6 μg/L). The As concentrations in the acetate and acetate + AQDS amended microcosms are of similar orders of magnitude to As concentrations in groundwaters from the aquifer sediment sampling site (127-170 nmol kg⁻¹). Arsenic concentrations in the sterilized control experiments were generally less than 15 nmol kg⁻¹ (1.1 μg/L), which is interpreted to be the amount of As released from Aquia aquifer sediments owing to abiotic, surface exchange processes. Iron concentrations released to solution in each of the microcosm experiments were higher and more variable than the As concentrations, but generally exhibited similar trends to the As concentrations. Specifically, the acetate and acetate + AQDS amended microcosm typically exhibited the highest Fe concentrations (up to 1725 and 6566 nmol kg⁻¹, respectively). The increase in both As and Fe in the artificial groundwater solutions in these amended microcosm experiments strongly suggests that microbes within the Aquia aquifer sediments mobilize As from the sediment substrate to the groundwaters via Fe(III) reduction.     

Rare earth elements (REE) and yttrium in stream waters, stream sediments, and Fe-Mn oxyhydroxides: Fractionation, speciation, and controls over REE + Y patterns in the surface environment

We have collected ∼500 stream waters and associated bed-load sediments over an ∼400 km² region of Eastern Canada and analyzed these samples for Fe, Mn, and the rare earth elements (REE + Y). In addition to analyzing the stream sediments by total digestion (multi-acid dissolution with metaborate fusion), we also leached the sediments with 0.25 M hydroxylamine hydrochloride (in 0.05 M HCl), to determine the REE + Y associated with amorphous Fe- and Mn-oxyhydroxide phases. We are thus able to partition the REE into “dissolved” (<0.45 μm), labile (hydroxylamine) and detrital sediment fractions to investigate REE fractionation, and in particular, with respect to the development of Ce and Eu anomalies in oxygenated surface environments. Surface waters are typically LREE depleted ([La/Sm]_NASC ranges from 0.16 to 5.84, average = 0.604, n = 410; where the REE are normalized to the North America Shale Composite), have strongly negative Ce anomalies ([Ce/Ce^∗]_NASC ranges from 0.02 to 1.25, average = 0.277, n = 354), and commonly have positive Eu anomalies ([Eu/Eu^∗]_NASC ranges from 0.295 to 1.77, average = 0.764, n = 84). In contrast, the total sediment have flatter REE + Y patterns relative to NASC ([La/Sm]_NASC ranges from 0.352 to 1.12, average = 0.778, n = 451) and are slightly middle REE enriched ([Gd/Yb]_NASC ranges from 0.55 to 3.75, average = 1.42). Most total sediments have negative Ce and Eu anomalies ([Ce/Ce^∗]_NASC ranges from 0.097 to 2.12, average = 0.799 and [Eu/Eu^∗]_NASC ranges from 0.39 to 1.43, average = 0.802). The partial extraction sediments are commonly less LREE depleted than the total sediments ([La/Sm]_NASC ranges from 0.24 to 3.31, average = 0.901, n = 4537), more MREE enriched ([Gd/Yb]_NASC ranges from 0.765 to 6.28, average = 1.97) and Ce and Eu anomalies (negative and positive) are more pronounced.The partial extraction recovered, on average ∼20% of the Fe in the total sediment, ∼80% of the Mn, and 21-29% of the REEs (Ce = 19% and Y = 32%). Comparison between REEs in water, partial extraction and total sediment analyses indicates that REEs + Y in the stream sediments have two primary sources, the host lithologies (i.e., mechanical dispersion) and hydromorphically transported (the labile fraction). Furthermore, Eu appears to be more mobile than the other REE, whereas Ce is preferentially removed from solution and accumulates in the stream sediments in a less labile form than the other REEs + Y. Despite poor statistical correlations between the REEs + Y and Mn in either the total sediment or partial extractions, based on apparent distribution coefficients and the pH of the stream waters, we suggest that either sediment organic matter and/or possibly δ-MnO₂/FeOOH are likely the predominant sinks for Ce, and to a lesser extent the other REE, in the stream sediments.     

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.