The effect of acid soil leaching on trace element abundance in a medium-sized stream,W. Finland

The concentration variations of 16 trace elements were determined along the main stem of a medium-sized stream (catchment area=107 km²), which drains areas covered with acid sulphate soils developed on sulphide-bearing marine sediments. During high flows in autumn, there was a strong downstream increase in the concentrations of Al, Cd, Co, Cu, Mn, Ni, Se, U and Zn and a moderate increase in those of Cr and Tl, related to extensive leaching of the acid sulphate soils, which increase in abundance from the headwater towards the basin outlet. During high flow in early summer, the downstream increase in the concentrations of these elements was not as strong as in autumn, due to decreased amounts of available mobile element fractions in the acid sulphate soils. Under baseflow conditions, the runoff from areas with acid sulphate soils is low in comparison to that in areas covered with other soils/sediments, resulting in relatively small loads of trace elements throughout the stream. The concentration variations of As, Pb, Sb, Ti and V were unrelated to catchment cover and did not vary along the stream in a regular manner. These 5 elements are, therefore, in contrast to the others, not leached more abundantly from the acid sulphate soils than from other soils/sediments. Based on the identified hydrogeochemical features and controls, it is suggested that water-quality improvement measures should include methods that primarily aim at reducing the leaching of hazardous chemical elements in the source areas (acid sulphate soils).     

Lanthanoid behaviour in an acidic landscape

Lanthanoids were studied in a boreal landscape where an abundance of acid sulfate soils and Histosols provide a unique opportunity to increase the understanding of how these metals behave in acidic soils and waters and interact with soil and aqueous organic matter. In the acid sulfate soils lanthanoids are mobile as reflected in high to very high concentrations in soil water and runoff (typically a few mg l⁻¹ but up to 12 mg l⁻¹) and abundant release by several relatively weak extractants (ammonium acetate EDTA, sodium pyrophosphate, hydroxylamine hydrochloride) applied on bulk soil. Normalisation with the lanthanoid pool in the underlying parent materials (sulphide-bearing sediments deposited in brackish-water) and soil water showed that the extensive release/retention in the acidic soil was accompanied by large, and variable, fractionation trends across the lanthanoid series. In low-order streams draining these soils, the lanthanoid concentrations were high and, as indicated by frontal ultrafiltration and geochemical modelling, largely dissolved (<1 kDa) in the form of the species LnSO₄⁺ and Ln³⁺. In other moderately acidic stream waters (pH 4.3-4.6), organic complexation was predicted to be important in the <1 kDa fraction (especially for the heavy lanthanoids) and strongly dominating in the colloidal phase (1 kDa-0.45 μm). Along the main stem of a stream in focus (catchment area of 223 km²), lanthanoid concentrations increased downstream, in particular during high flows, caused by a downstream increase in the proportion of acid sulfate soils which are extensively flushed during wet periods. The geochemical models applied to the colloidal Ln-organic phase were not successful in predicting the measured fractionation patterns.     

Dynamics of contaminants in phosphogypsum of the fertilizer industry of Huelva (SW Spain): From phosphate rock ore to the environment

The dynamics of trace elements from phosphate rock ore to the environment in a phosphoric acid plant located in SW Spain and the impact of phosphogypsum wastes were investigated through total digestion and BCR-sequential extraction. Based on total concentration, element transfer factors as criteria for examining the potential environmental risk of waste with respect to ore rock were calculated, and it was observed that most trace elements are only transferred into phosphogypsum at rates of 2–12%. However, based on those concentrations that are likely to be most readily mobile in the environment, phosphogypsum acts as a higher emission source of contaminants than the original rock. About 100 million tonnes of phosphogypsum are stack-piled in a dump of 1200 ha over salt-marshes of an estuary formed by the confluence of the Tinto and Odiel rivers. Phosphogypsum has been applied, at the recommended rate of 20–25 t/ha since 1978–2001, to improve fertility and reduce Na saturation in agricultural soils of the Guadalquivir river valley (140 km²). Phosphogypsum capacity as a source of mobile contaminants in three environmental scenarios (water leaching, exposure to oxidising and reducing conditions) was quantified by combining sequential extraction and waste mass. The amounts of mobile contaminants that could be released for every tonne of phosphogypsum are approximately 7 × 10² g Sr, 1.1 × 10² g Fe, 55 g Y, 30 g Ce, 12 g Cr, 11 g Ti, 5 g Zn, 4 g each of Cu and Pb, 3 g each of V and Cd, 2 g each of As and Ni and 1 g U. Multiplying these amounts by 100 Mt and 20–25 t/ha, it is possible to calculate risk assessments of phosphogypsum for both estuarine zones, e.g. in a hypothetical stack collapse and waste spilling, and agricultural soils, respectively.     

Chemical weathering in the Hong (Red) River basin: Rates of silicate weathering and their controlling factors

The Hong (Red) River drains the prominent Red River Fault Zone that has experienced various tectonic activities—intrusion of magma, exhumation of basement rocks, and influx of thermal waters—associated with the Cenozoic collision of India and Eurasia. We report dissolved major element and Sr isotope compositions of 43 samples from its three tributary systems (Da, Thao/Hong main channel, and Lo) encompassing summer and winter seasons. Carbonic acid ultimately derived from the atmosphere is the main weathering agent, and sulfuric acid from pyrite oxidation plays a minor role. Seasonality is manifested in higher calcite saturation index and Mg/TZ⁺ and lower Ca/Mg in summer, suggesting calcite precipitation, and in higher Si/(Na^∗ + K) ratios in summer suggesting more intensive silicate weathering. We quantified the input from rain, evaporite, carbonate, and silicate reservoirs using forward and inverse models and examined the robustness of the results. Carbonate dissolution accounts for a significant fraction of total dissolved cations (55-97%), and weathering of silicates makes a minor contribution (1-40%). Our best estimate of the spatially averaged silicate weathering rate in the Hong basin is 170 × 10³ mol/km²/yr in summer and 51 × 10³ mol/km²/yr in winter. We tested for correlations between the rate of CO₂ consumption by silicate weathering and various climatic (air temperature, precipitation, runoff, and potential evapotranspiration) and geologic (relief, elevation, slope, and lithology) parameters calculated using GIS. Clear correlations do not emerge (except for ?CO₂ and runoff in winter) which we attribute to the complex geologic setting of the area, the seasonal regime change from physical-dominant in summer to chemical-dominant in winter, and the incoherent timescales involved for the different parameters tested.     

Sulphide-mining impacts in the physical environment: Sierra de Cartagena–La Unión (SE Spain) case study

The environmental impact and potential-risk assessment of an abandoned sulphide-mining site in a semiarid climate is presented here, by the study case of Sierra de Cartagena–La Unión (SE Spain), a 2,500-year-old mining district extending over an area of 100 km². The regional map illustrates the existence of 12 open-pits, 1,902 mining wells, 2,351 waste deposits, including 89 tailing dams and waste rock derived from mining processes. Mine wastes occupy an area of 9 km² and have an approximate volume of 200 Mm³. Mineralogical, physical and chemical data distinguish nine different types of mine and metallurgical waste. According to the concentration of sulphate and heavy metals in sediment, soil, rainwater, surface water and groundwater samples, it is possible to conclude that the impact of mine activities occurs not only in the immediate mining area (100 km²), but also in the surrounding areas (an affected area of 1,000 km² approximately). The hydrochemical data show that groundwater, runoff water and some rainwater samples exceed Spanish and European water quality guideline values for water supply. The main geochemical process recognised is sulphide-mineral oxidation and later-generated sulphate dissolution by groundwater and runoff. Runoff and wind are the major mechanisms of metals and sulphate transport in the study area and adjacent zones.     

Hydrochemistry of the Natuf drainage basin in Ramallah area/West Bank

The Natuf drainage basin in the western hills of Ramallah district is about 200 km² _. Many springs emerge in the area from perched aquifers and outcrop from limestone and dolomite limestone formations. This study aims to add more information about hydrochemical parameters and the chemical changes in spring water between dry and wet seasons and to locate possible sources of pollution and their effect on the water quality of water from the springs for domestic and agricultural uses. The study involved collection and analysis by conventional and available instrumental methods for the hydrochemical parameters from 12 springs before and after recharge. Water samples of runoff from two places in eastern and western parts of the study area were collected and analyzed as well. Most of the springs in the study area are of good water quality for domestic and agricultural uses. Variations in the chemical composition between dry and wet seasons, and from one spring to another, were observed. Springs near densely populated areas and agricultural activities show higher values of EC, SSP, SAR and TH. Also uncountable colonies of faecal- and total coliform were detected. Trace amounts, within World Health Organization (WHO) and the Palestinian standard limits, of cadmium, chromium, cobalt and lead are found in some springs; while concentrations of iron and zinc that were detected in springs near populated areas are higher than other springs. Water types of Ein Musbah, Al Alaq and Ein Arik El Tehta are of earth alkaline with increased portion of alkalis with prevailing bicarbonate and chloride in wet and dry seasons. Other springs show a variation in water type between earth alkaline with prevailing bicarbonate in the wet seasons to earth alkaline with prevailing bicarbonate and chloride in the dry seasons.

Seasonal variability in the input of lead, barium and indium to Law Dome, Antarctica

Lead (Pb) isotopic compositions and concentrations, and barium (Ba) and indium (In) concentrations have been determined at monthly resolution in five Law Dome (coastal Eastern Antarctica) ice core sections dated from ∼1757 AD to ∼1898 AD. ‘Natural’ background Pb concentrations in ∼1757 AD average ∼0.2 pg g⁻¹ and can be attributed to mineral dust and volcanic emissions, with ²⁰⁶Pb/²⁰⁷Pb ratios reaching up to 1.266 ± 0.002. From ∼1887 AD to ∼1898 AD, Pb concentrations reached ∼5 pg g⁻¹ and ²⁰⁶Pb/²⁰⁷Pb ratios decreased to 1.058 ± 0.001 as a result of additional inputs of Pb from anthropogenic sources. Seasonal variability in the late 1880s has been investigated by decoupling volcanic Pb from the total measured Pb concentrations, revealing spring and autumn maxima, and consistent winter minima, in anthropogenic Pb and mineral dust (Ba) concentrations. We link this variability to the annual cycle in the position and strength of the Antarctic Circumpolar Trough and, the Southern Ocean westerly winds to the north of the trough region. During the autumn and spring seasons, these systems increase in strength, transporting more impurity laden air from the Southern Hemisphere continental regions to Eastern Antarctica and Law Dome. As this Pb is isotopically identical to that emitted from south-eastern Australia (Broken Hill, Port Pirie) this implies a relatively direct air trajectory pathway from southern Australia to Law Dome (Eastern Antarctica).     

Selenium levels in Lebanese environment

Very limited research has been conducted on selenium (Se) in Lebanese soils and forage crops but no work has been done on Se in water and locally produced vegetables and grains. This research was conducted in order to quantify Se levels and its availability in agricultural soils, vegetables and grains in Lebanon. Sixty-six (66) soil samples were collected from 33 selected sites in Lebanon: the Bekaa Valley, coastal and mountainous regions. Thirteen (13) different plant types (86 samples) were sampled from the same locations. Also, 13 spring water and 10 bottled water samples were collected. Soil samples were analyzed for their physical and chemical properties. Selenium was extracted from soils with: deionized–distilled water (Soluble-Se), KH₂PO₄-0.1 M (MKP-Se) and concentrated (HNO₃ + HCl) mixture (acid-Se). Plant Se was extracted by acid digestion on a hotplate. Selenium concentrations were measured by the inductively coupled plasma-mass spectrophotometer (ICP-MS). The values of Soluble-Se, MKP-Se and acid-Se ranged between 47 and 142, 147 and 400, and 1749 and 4713 μg/kg, respectively, with average values of 95, 306, and 3118 μg/kg and at a ratio of 1:3:30. Thus, Se extracted with deionized–distilled water is a good indicator for Se availability in the studied soils. The average Se concentration in plants was in the following order: radish > lettuce > cucumber > cabbage > parsley > alfalfa > onion (leaves) > broccoli > tomato > mint > chickpeas > wheat > onion (bulbs). The Se levels in water samples were in the safe range (less than 50 μg/L) and ranged between 2.14 and 17.6 μg/L. The levels of Se in the three soil extractants were positively correlated with each other and with organic matter content, salinity and phosphorus (P). Selenium levels in plant samples were positively correlated at a 0.01 significance level with clay and P content.     

Fluxes of high- versus low-temperature water-rock interactions in aerial volcanic areas: Example from the Kamchatka Peninsula, Russia

Volcanic areas play a key role in the input of elements into the ocean and in the regulation of the geological carbon cycle. The aim of this study is to investigate the budget of silicate weathering in an active volcanic area. We compared the fluxes of the two major weathering regimes occurring at low temperature in soils and at high temperature in the active volcanic arc of Kamchatka, respectively. The volcanic activity, by inducing geothermal circulation and releasing gases to the surface, produces extreme conditions in which intense water-rock interactions occur and may have a strong impact on the weathering budgets. Our results show that the chemical composition of the Kamchatka river water is controlled by surface low-temperature weathering, atmospheric input and, in some limited cases, strongly imprinted by high-temperature water-rock reactions. We have determined the contribution of each source and calculated the rates of CO₂ consumption and chemical weathering resulting from low and high-temperature water/rock interactions. The weathering rates (between 7 and 13.7 t/km²/yr for cations only) and atmospheric CO₂ consumption rates (∼0.33-0.46 × 10⁶ mol/km²/yr for Kamchatka River) due to rock weathering in soils (low-temperature) are entirely consistent with the previously published global weathering laws relating weathering rates of basalts with runoff and temperature. In the Kamchatka River, CO₂ consumption derived from hydrothermal activity represents about 11% of the total HCO₃ flux exported by the river. The high-temperature weathering process explains 25% of the total cationic weathering rate in the Kamchatka River. Although in the rivers non-affected by hydrothermal activity, the main weathering agent is carbonic acid (reflected in the abundance of in rivers), in the region most impacted by hydrothermalism, the protons responsible for minerals dissolution are provided not only by carbonic acid, but also by sulphuric and hydrochloric acid. A clear increase of weathering rates in rivers impacted by sulphuric acid can be observed. In the Kamchatka River, 19% of cations are released by hydrothermal acids or the oxidative weathering of sulphur minerals.Our results emphasise the important impact of both low and high-temperature weathering of volcanic rocks on global weathering fluxes to the ocean. Our results also show that besides carbonic acid derived from atmospheric CO₂, hydrochloric acid and especially sulphuric acid are important weathering agents. Clearly, sulphuric acid, with hydrothermal activity, are key parameters that cause first-order increases of the chemical weathering rates in volcanic areas. In these areas, accurate determination of weathering budgets in volcanic area will require to better quantify sulphuric acid impact.     

Antimony in the environment: Lessons from geochemical mapping

The distribution of Sb in a variety of sample materials, including soils, plants and surface water, was studied at different scales, from continental to local, combining published data sets with the aim of delineating the impact and relative importance of geogenic vs. anthropogenic Sb sources. Geochemical mapping demonstrates that variation is high at all scales – from the detailed scale with sample densities of many sites per km² to the continental-scale with densities of 1 site per 5000 km². Different processes govern the Sb distribution at different scales. A high sample density of several samples per km² is needed to reliably detect mineralisation or contamination in soil samples. Median concentrations are so low for Sb in most sample materials (below 1 mg/kg in rocks and soils, below 0.1 mg/kg in plants, below 0.1 μg/L in surface water) that contamination is easier to detect than for many other elements. Distribution patterns on the sub-continental to continental-scale are, however, still dominated by natural variation. Given that the geochemical background is characterised by a high variation at all scales, it appears impossible to establish a reliable single value for “good soil quality” or a “natural background concentration” for Sb for any sizeable area, e.g., for Europe. For such a differentiation, geochemical maps at a variety of scales are needed.     

Metal speciation in rivers affected by enhanced soil erosion and acidity

Dissolved (<1 kDa), colloidal (1 kDa–0.45 μm) and particulate (>0.45 μm) size fractions of 30 elements were determined for four rivers (Sirppujoki, Laajoki, Mynäjoki and Paimionjoki), including 12 low-order inflow streams, largely affected by soil erosion and acidity in SW Finland. In addition, geochemical modelling was used to predict the formation of free ions and complexes in these rivers. Total metal concentrations were relatively high but most of the elements occurred mainly in a colloidal or particulate form and even elements expected to be very soluble occurred to a large extent in colloidal form. According to geochemical modelling these patterns could be explained by in-stream metal complexation/adsorption only to a limited extent. Instead there were strong indications that the high metal concentrations and dominant solid fractions were largely caused by erosion of metal bearing phyllosilicates. A strong influence of acid sulphate (AS) soils, known to exist in the catchment, could be clearly distinguished in Sirppujoki river as it had very high concentrations of dissolved metals, while in the two nearby rivers (Laajoki and Mynäjoki) the influence of AS soils was largely masked by eroded phyllosilicates. In Paimionjoki river the colloidal and particulate fractions dominated very strongly, indicating that total metal concentrations are almost solely controlled by erosion of phyllosilicates. Consequently, rivers draining clay plains sensitive to erosion, like those in SW Finland, have generally high “background” metal concentrations due to erosion of relatively non-toxic colloidal/particulate phyllosilicates. Thus, relying on only semi-dissolved (<0.45 μm) concentrations obtained in routine monitoring and/or speciation modelling can lead to a great overestimation of the water toxicity in this environment.     

Hydrological basis of the Devils Lake,North Dakota (USA), terminal lake flood disaster

Devils Lake, a terminal lake in northeast North Dakota (USA), has experienced catastrophic flooding since 1993. From January 31, 1993, to December 31, 2014, lake level rose from 433.62 to 442.44 m, lake area expanded from 179.9 to 653.5 km², and lake volume increased from 0.70 to 3.80 km³. More than $1 billion ($USD) has been spent in government payments to mitigate direct, primary, tangible flood damages. This paper provides a case study of the hydrological basis of the Devils Lake flood disaster. The unique geomorphic setting, paleoclimatic record, and hydroclimatic conditions of the region are summarized, and a wide range of hydroclimatic data is examined to provide a broad understanding of the physical basis of the flood disaster. The primary cause of the disaster was a transition to a sustained wetter climate that resulted in a dramatic response in basin hydrological variables in 1993. The transition from a long-term dry period to a long-term wet period caused the lake water budget to begin to change from an atmosphere-controlled water budget dominated by precipitation input to an amplifier lake water budget dominated by surface runoff input to the lake. Other important hydrological factors include a nonlinear precipitation–runoff relationship following the long-term drought, fill-spill and fill-merge hydrological behavior that is characteristic of wetland complexes, an increase in the lake area-to-basin area ratio, and the critical role of frozen soils in controlling infiltration and runoff production of spring snowmelt. Engineering works to manage lake volume through two outlets have reduced, but not entirely eliminated, future flood risk.

     

Chemical weathering in the plain and peninsular sub-basins of the Ganga: Impact on major ion chemistry and elemental fluxes

Concentrations of major ions, Sr and ⁸⁷Sr/⁸⁶Sr have been measured in the Gomti, the Son and the Yamuna, tributaries of the Ganga draining its peninsular and plain sub-basins to determine their contribution to the water chemistry of the Ganga and silicate and carbonate erosion of the Ganga basin. The results show high concentrations of Na and Sr in the Gomti, the Yamuna and the Ganga (at Varanasi) with much of the Na in excess of Cl. The use of this ‘excess Na’ (Na∗ = Na_riv − Cl_riv) a common index of silicate weathering yield values of ∼18 tons km⁻² yr⁻¹ for silicate erosion rate (SER) in the Gomti and the Yamuna basins. There are however, indications that part of this Na∗ can be from saline/alkaline soils abundant in their basins, raising questions about its use as a proxy to determine SER of the Ganga plain. Independent estimation of SER based on dissolved Si as a proxy give an average value of ∼5 tons km⁻² yr⁻¹ for the peninsular and the plain drainages, several times lower than that derived using Na∗. The major source of uncertainty in this estimate is the potential removal of Si from rivers by biological and chemical processes. The Si based SER and CER (carbonate erosion rate) are also much lower than that in the Himalayan sub-basin of the Ganga. The lower relief, runoff and physical erosion in the peninsular and the plain basins relative to the Himalayan sub-basin and calcite precipitation in them all could be contributing to their lower erosion rates.Budget calculations show that the Yamuna, the Son and Gomti together account for ∼75% Na, 41% Mg and ∼53% Sr and ⁸⁷Sr of their supply to the Ganga from its major tributaries, with the Yamuna dominating the contribution. The results highlight the important role of the plain and peninsular sub-basins in determining the solute and Sr isotope budgets of the Ganga. The study also shows that the anthropogenic contribution accounts for ?10% of the major ion fluxes of the Ganga at Rajmahal during high river stages (October). The impact of both saline/alkaline soils and anthropogenic sources on the major ion abundances of the Ganga is minimum during its peak flow and therefore the SER and CO₂ consumption rates of the river is best determined during this period.     

Weathering and the mobility of phosphorus in the catchments and forefields of the Rhône and Oberaar glaciers, central Switzerland: Implications for the global phosphorus cycle on glacial-interglacial timescales

In this study we evaluate the dynamics of the biophile element phosphorus (P) in the catchment and proglacial areas of the Rhône and Oberaar glaciers (central Switzerland). We analysed erosion and dissolution rates of P-containing minerals in the subglacial environment by sampling water and suspended sediment in glacier outlets during three ablation and two accumulation seasons. We also quantified biogeochemical weathering rates of detrital P in proglacial sedimentary deposits using two chronosequences of samples of fresh, suspended, material obtained from the Oberaar and Rhône water outlets, Little-Ice-Age (LIA) moraines and Younger Dryas (YD) tills in each catchment. Subglacial P weathering is mainly a physical process and detrital P represents more than 99% of the precipitation-corrected total P denudation flux (234 and 540 kg km⁻² yr⁻¹ for the Rhône and Oberaar catchments, respectively). The calculated detrital P flux rates are three to almost five times higher than the world average flux. The precipitation-corrected soluble reactive P (SRP) flux corresponds to 1.88-1.99 kg km⁻² yr⁻¹ (Rhône) and 2.12-2.44 kg km⁻² yr⁻¹ (Oberaar), respectively. These fluxes are comparable to those of tropical rivers draining transport-limited, tectonically inactive weathering areas.In order to evaluate the efficiency of detrital P weathering in the Rhône and Oberaar proglacial areas, we systematically graded apatite grains extracted from the chronosequence in each catchment relative to weathering-induced changes in their surface morphologies (grades 1-4). Fresh apatite grains are heavily indented and dissolution rounded (grade 1). LIA grains from two 0-10 cm deep moraine samples show extensive dissolution etching, similar to surface grains from the YD profile (mean grades 2.7, 3.5 and 3.5, respectively). In these proglacial deposits, the weathering front deepens progressively as a function of time due to biocorrosion in the evolving acidic pedosphere, with mechanical indentations on grains acting as sites of preferential dissolution. We also measured iron-bound, organic and detrital P concentrations in the chronosequence and show that organic and iron-bound P has almost completely replaced detrital P in the top layers of the YD profiles. Detrital P weathering rates are calculated as 310 and 280 kg km⁻² yr⁻¹ for LIA moraines and 10 kg km⁻² yr⁻¹ for YD tills. During the first 300 years of glacial sediment exposure P dissolution rates are shown to be approximately 70 times higher than the mean global dissolved P flux from ice-free continents. After 11.6 kyr the flux is 2.5 times the global mean. These data strengthen the argument for substantial changes in the global dissolved P flux on glacial-interglacial timescales. A crude extrapolation from the data described here suggests that the global dissolved P flux may increase by 40-45% during the first few hundred years of a deglaciation phase.     

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.     

Field multi-step limestone and MgO passive system to treat acid mine drainage with high metal concentrations

Passive treatment systems have become one of the most sustainable and feasible ways of remediating acid mine drainage (AMD). However, conventional treatments show early clogging of the porosity or/and coating of the reactive grains when high acidity and metal concentrations are treated. The performance of fine-grained reagents dispersed in a high porosity matrix of wood shavings was tested as an alternative to overcome these durability problems. The system consisted of two tanks of 3 m³ filled with limestone sand and wood shavings, and one tank of 1 m³ with caustic magnesia powder and wood shavings, separated by several oxidation cascades and decantation ponds. The system treated about 1.5 m³/day of AMD containing an average of 360 mg/L Fe, 120 mg/L Al, 390 mg/L Zn, 10 mg/L Cu, 300 μg/L As and 140 μg/L Pb, a mean pH of 3.08 and a net acidity of 2500 mg/L as CaCO₃ equivalent. The water reached pH 5 and 6 in the first and second limestone tanks, respectively (suitable to remove trivalent metals); and pH 8–9 in the MgO tank (suitable to remove divalent metals). After 9 months of operation, the system achieved an average removal of 100% Al, Cu, As, Pb, more than 70% Fe, about 25% Zn and 80% acidity. Goethite, schwertmannite, hydrobasaluminite, amorphous Al(OH)₃ and gypsum were the main precipitates in the two limestone tanks. Precipitation of divalent metals (Fe (II), Zn, and traces of Cd, Ni and Co) were complete inside the third tank of MgO, but preferential flow along the walls was responsible for its low treatment performance. Goethite, gypsum, Zn-schulenbergite and sauconite are the crystalline solid phases identified in the MgO tank.     

青藏高原东南缘迪庆地区年季蒸发皿蒸发、降水和径流深分析

利用青藏高原东南边缘核心区迪庆地区3个站的蒸发皿蒸发、降水、径流深观测资料,分析了各要素年内、年际变化规律,检验了突变点,探讨了区域蒸发、降水、径流深相关关系。结果表明：（1）研究区蒸发量年内四季分布相对均衡,其次为径流深及降水量;径流深年际离散系数低,其次为降水量、蒸发量;径流深年内季节分布年际离散系数低,其次为蒸发量、降水量。（2）研究区年度蒸发量的增加主要因春季蒸发增加,年度降水量的减少主要因冬季降水量减少,年度径流深的增加主要因夏季、秋季、冬季径流深增加所致,夏季径流深增加主要因夏季蒸发减少,秋季径流深增加主要因秋季降水增加、蒸发减少、夏季径流增加、蒸发减少所致,冬季径流深增加主要因秋季径流增加所致。（3）研究区年度、春季蒸发量下降趋势显著,年度干旱、春旱风险呈降低趋势;降水量年内占比趋向于向夏季、秋季集中,径流深夏、秋季呈增加趋势,区域内洪涝灾害风险有增大趋势。2000年以来,区域内年度蒸发量出现较为明显增加趋势,年度降水量、年度径流出现明显减少趋势,该趋势与线性趋势出现背离,且年度和四季降水量、径流深在2014年左右均检测出变少突变信号,该现象可能对区域生态环境及水资源状况产生较大影响。     

Stable sulfur and oxygen isotope ratios of the Świętokrzyski National Park spring waters generated by natural and anthropogenic factors (south-central Poland)

This paper presents the results of an isotopic study of spring waters in ?wi?tokrzyski (Holy Cross Mountain) National Park (?NP), south-central Poland. The δ³⁴S_V-CDT and δ¹⁸O_V-SMOW of soluble sulfates (n = 40) varied from 0.5‰ to 18.1‰ and from 3.5‰ to 12.2‰, respectively. The average δ³⁴S values are closely similar to those of rainwater, soils and rocks (comprising scattered pyrite). This suggests that soluble sulfates in the springs originated from mixing of recent and historic deposition, sulfates derived from pyrite oxidation, and CS-mineralization in soils and debris. An additional anthropogenic sulfur input (inorganic fertilizer) occurs in the water of spring S-61 located in the ?wi?tokrzyski National Park buffer zone. The δ¹⁸O_V-SMOW of spring waters (n = 4) were in the range of −10.6‰ to −10.2‰ indicating that they are derived from vadose groundwater in ?NP. This was the first isotope study of spring waters in the national parks of Poland. It enabled the determination of sulfur pathways and discrimination between natural and anthropogenic sources of this element in a relatively pristine area.     

The role of rare rainstorms in the formation of calcic soil horizons on alluvial surfaces in extreme deserts

Soils in similar geomorphic settings in hyperarid deserts (< 50 mm yr⁻¹) should have similar characteristics because a negative moisture balance controls their development. However, Reg soils in the hyperarid southern Negev and Namib deserts are distinctly different. Soils developed on stable alluvial surfaces with only direct input of rainfall and dust depend heavily on rainfall characteristics. Annual rainfall amount can be similar (15-30 mm), but storm duration can drastically alter Reg soil properties in deserts. The cooler fall/winter and dry hot summers of the southern Negev Desert with a predominance brief (≤ 1 day) rainstorms result in gypsic-saline soils without any calcic soil horizon. Although the Namib Desert receives only 50-60% of the southern Negev annual rainfall, its rainstorm duration is commonly 2-4 days. This improves leaching of the top soil under even lower annual rainfall amount and results in weeks-long grass cover. The long-term cumulative effect of these rare rain-grass relationships produces a calcic-gypsic-saline soil. The development of these different kinds of desert soils highlights the importance of daily to seasonal rainfall characteristics in influencing soil-moisture regime in deserts, and has important implications for the use of key desert soil properties as proxies in paleoclimatology.