Chemical speciation in mining affected waters: the case study of Asarel-Medet mine

The inorganic chemical species in Maresh and Luda Yana rivers affected by the Cu– Mo Asarel-Medet mine, Bulgaria were determined during a low-flow and a high-flow period. The mining activities, the weathering and the oxidation processes strongly influenced the physicochemical processes in the whole water system. The main pollution source was a small lake receiving the acid effluents of the mining activities. High levels of SO₄ ^2???, Cu, Mg, Al, Mn and Fe were determined at the mining polluted and affected stations. Cu^2?+? and CuCO₃ ⁰ species (1:1) were present in the reference waters and Cu^2?+? and CuSO₄ ⁰ species (1:1) in the polluted and affected waters; Cu^2?+? species was dominating downstream. Me^2?+? followed by $\rm{MeSO}_{4}^{\kern3pt{0}}$ (Me = Mn, Zn, Cd and Pb), $\rm{PbCO}_{3}^{\kern3pt{0}}$ and $\rm{PbHCO}_{3}^{\kern3pt{+}}$ species as well as $\rm{Fe(OH)}_{2}^{\kern3pt{+}}$ , $\rm{Al(OH)}_{4}^{\kern3pt{-}}$ , $\rm{Al(OH)}_{2}^{\kern3pt{+}}$ , $\rm{Al(OH)}_{3}^{\kern3pt{0}}$ were prevailing in the system. $\rm{MeSO}_{4}^{\kern3pt{+}}$ and $\rm{Me(SO}_{4})_{2}^{\kern3pt{-}}$ (Me = Fe, Al), $\rm{Me(SO}_{4})_{2}^{\kern3pt{2-}}$ (Me = Zn, Cd and Pb), $\rm{Me(SO}_{4})_{3}^{\kern3pt{4-}}$ (Me = Zn, Cd) and $\rm{Cd(SO}_{4})_{4}^{\kern3pt{6-}}$ species polluted and affected waters. The major elements K and Na were mainly Me^?+? species, whereas Ca and Mg were Me^2?+? and $\rm{MeSO}_{4}^{\kern3pt{0}}$ species in different ratios. The concentration of concentration of $\rm{NO}_{2}^{\kern3pt{-}}$ , $\rm{NO}_{3}^{\kern3pt{-}}$ and $\rm{NH}_{4}^{\kern3pt{+}}$ species as well as complex phosphorous species such as H₂ $\rm{PO}_{4}^{\kern3pt{-}}$ , $\rm{FeHPO}_{4}^{\kern3pt{+}}$ , $\rm{HPO}_{4}^{\kern4pt{2-}}$ , $\rm{CaPO}_{4}^{\kern3pt{-}}$ , $\rm{CaHPO}_{4}^{\kern3pt{0}}$ and $\rm{MgHPO}_{4}^{\kern3pt{0}}$ were also calculated. The trace element concentrations decreased downstream due to dilution, sorption processes and precipitation, but the percentage of free metal species, which are more toxic, increased. An exception was iron and aluminum of which the dominant hydroxy colloidal and sulphate species were easily incorporated into the suspended phase.     

Comparison of precipitation chemistry measurements obtained by the Canadian Air and Precipitation Monitoring Network and National Atmospheric Deposition Program for the period 1995–2004

Precipitation chemistry and depth measurements obtained by the Canadian Air and Precipitation Monitoring Network (CAPMoN) and the US National Atmospheric Deposition Program/National Trends Network (NADP/NTN) were compared for the 10-year period 1995–2004. Colocated sets of CAPMoN and NADP instrumentation, consisting of precipitation collectors and rain gages, were operated simultaneously per standard protocols for each network at Sutton, Ontario and Frelighsburg, Ontario, Canada and at State College, PA, USA. CAPMoN samples were collected daily, and NADP samples were collected weekly, and samples were analyzed exclusively by each network’s laboratory for pH, H^?+?, Ca^2?+?, Mg^2?+?, Na^?+?, K^?+?, $\text{NH}_{4}^{+}$ , Cl^???, $\text{NO}_{3}^{-}$ , and $\text{SO}_{4}^{2-}$ . Weekly and annual precipitation-weighted mean concentrations for each network were compared. This study is a follow-up to an earlier internetwork comparison for the period 1986–1993, published by Alain Sirois, Robert Vet, and Dennis Lamb in 2000. Median weekly internetwork differences for 1995–2004 data were the same to slightly lower than for data for the previous study period (1986–1993) for all analytes except $\text{NO}_{3}^{-}$ , $\text{SO}_{4}^{2-}$ , and sample depth. A 1994 NADP sampling protocol change and a 1998 change in the types of filters used to process NADP samples reversed the previously identified negative bias in NADP data for hydrogen-ion and sodium concentrations. Statistically significant biases (α = 0.10) for sodium and hydrogen-ion concentrations observed in the 1986–1993 data were not significant for 1995–2004. Weekly CAPMoN measurements generally are higher than weekly NADP measurements due to differences in sample filtration and field instrumentation, not sample evaporation, contamination, or analytical laboratory differences.     

Interseasonal hydrological characteristics and variabilities in surface water of tropical estuarine ecosystems within Niger Delta, Nigeria

We present a seasonal and baseline survey of selected physicochemical parameters in epipelagic samples from Qua Iboe (QIB) and Cross River (CRV) estuaries in Niger Delta region of Nigeria. The parameters analysed were temperature, pH, salinity, turbidity, total suspended solids (TSS), dissolved oxygen (DO), biochemical oxygen demand (BOD), total organic carbon (TOC), total nitrogen, available phosphorus, Ca^2?+?, Mg^2?+?, Na^?+?, K^?+? (exchangeable cations) and ${\rm SO}_{4}^{2-}$ , Cl^???, ${\rm NH}_{4}^{+}$ and ${\rm NO}_{3}^{-}$ . The results showed that the physicochemical parameters exhibited spatiotemporally explicit variabilities. The mean levels of the parameters were higher during the wet season (June–September) except salinity, DO, Cl^??? and ${\rm NH}_{4}^{+}$ in CRV, whilst QIB recorded higher mean levels for temperature, pH, salinity, BOD, TOC, ${\rm SO}_{4}^{2-}$ , Cl^??? and ${\rm NH}_{4}^{+}$ during the dry season (November–February). Significant seasonal variability was recorded for salinity, DO, turbidity, TSS, ${\rm SO}_{4}^{2-}$ and ${\rm NH}_{4}^{+}$ levels in CRV and for turbidity, DO, BOD, TSS, TOC, available P, Na, Cl^??? and ${\rm NO}_{3}^{-}$ levels in QIB. This study confirmed that the degree of variability of the various physicochemical surface water quality indicators is dependent on the prevalent environmental estuarine factors.     

Chemical speciation in waters influenced by lead–zinc metallurgical industry

The Lead–Zinc Company region, Kardjali city, Bulgaria, is known to be highly polluted with heavy metals from its pyrometallurgical activities. The polluted levels and the chemical speciation in surface natural waters in the region as well as in the wastewaters of the factory were investigated in January 2008 by application of monitoring studies, thermodynamic modeling, and interpretation in terms of the “softness–hardness” factor. It was found that the levels of trace metals pollution of surface waters were lower than the legislation limits for the regions with Pb and Zn production. The wastewater treatment facilities of the company were found to operate properly, and the quality of the cleaned waters in station Kar4 was comparable to the other surface waters studied (e.g., station Kar5). The trace metals were divided into three groups: (1) Fe^3?+? and Al^3?+?, being “hard” acids, existed in all the studied waters as hydroxy species Fe(OH) $_{2}^{+}$ , AlOH^2?+?, and Al(OH) $_{2}^{+}$ , followed by the phosphate species AlPO $_{4}^{0}$ and Al₂(OH)₂PO $_{4}^{+}$ ; (2) Mn^2?+?, Zn^2?+?, and Cd^2?+? being “soft” acids with crystal field stabilization energy (CFSE) = 0 were present in natural waters mainly as free Me^2?+? ions. Small concentrations of their MeSO $_{4}^{0}$ , MeCO $_{3}^{0}$ species, and of MeCl $_{2}^{0}$ (Me = Zn, Cd) species were also calculated. In the wastewaters, two more species [Me(SO $_{4})_{2}^{2-}$ and Me(SO $_{4})_{3}^{4-}$ ] of the softer Zn and Cd metals were also calculated; (3) Cu^2?+? and Pb^2?+?, as “soft” acids with CFSE $\ne $ 0 preferentially coordinated with softer CO $_{3}^{2-}$ ions and in natural waters existed mainly as MeCO $_{3}^{0}$ and PbHCO $_{3}^{+}$ , followed by free Me^2?+?ions and MeOH^?+?. In the wastewaters, MeSO $_{4}^{0}$ and Pb(SO $_{4})_{2}^{2-}$ species increased at the expense of the free Me^2?+? ions. The highest self-cleaning capability of natural waters was found with respect to Al and Fe, followed by Mn and Cd. The lowest corresponded to Pb, Cu, and Zn.     

Twenty-year inter-annual trends and seasonal variations in precipitation and stream water chemistry at the Bear Brook Watershed in Maine, USA

Mean annual concentration of ${\textrm{SO}}_{4}^{2-}$ in wet-only deposition has decreased between 1988 and 2006 at the paired watershed study at Bear Brook Watershed in Maine, USA (BBWM) due to substantially decreased emissions of SO₂. Emissions of NO_x have not changed substantially, but deposition has declined slightly at BBWM. Base cations, ${\textrm{NH}}_{4}^{+}$ , and Cl^??? concentrations were largely unchanged, with small irregular changes of <1 μeq L^???1 per year from 1988 to 2006. Precipitation chemistry, hydrology, vegetation, and temperature drive seasonal stream chemistry. Low flow periods were typical in June–October, with relatively greater contributions of deeper flow solutions with higher pH; higher concentrations of acid-neutralizing capacity, Si, and non-marine Na; and low concentrations of inorganic Al. High flow periods during November–May were typically dominated by solutions following shallow flow paths, which were characterized by lower pH and higher Al and DOC concentrations. Biological activity strongly controlled ${\textrm{NO}}_{3}^{-}$ and K^?+?. They were depressed during the growing season and elevated in the fall. Since 1987, East Bear Brook (EB), the reference stream, has been slowly responding to reduced but still elevated acid deposition. Calcium and Mg have declined fairly steadily and faster than ${\textrm{SO}}_{4}^{2-}$ , with consequent acidification (lower pH and higher inorganic Al). Eighteen years of experimental treatment with (NH₄)₂SO₄ enhanced acidification of West Bear Brook’s (WB) watershed. Despite the manipulation, ${\textrm{NH}}_{4}^{+}$ concentration remained below detection limits at WB, while leaching of ${\textrm{NO}}_{3}^{-}$ increased. The seasonal pattern for ${\textrm{NO}}_{3}^{-}$ concentrations in WB, however, remained similar to EB. Mean monthly concentrations of ${\textrm{SO}}_{4}^{2-}$ have increased in WB since 1989, initially only during periods of high flow, but gradually also during base flow. Increases in mean monthly concentrations of Ca^2?+?, Mg^2?+?, and K^?+? due to the manipulation occurred from 1989 until about 1995, during the depletion of base cations in shallow flow paths in WB. Progressive depletion of Ca and Mg at greater soil depth occurred, causing stream concentrations to decline to pre-manipulation values. Mean monthly Si concentrations did not change in EB or WB, suggesting that the manipulation had no effect on mineral weathering rates. DOC concentrations in both streams did not exhibit inter- or intra-annual trends.     

Leaching of nitrogen from calcareous soils in western Iran: a soil leaching column study

Nitrogen (N) leaching has become a matter of worldwide concern. The objectives of this study were: (1) to use soil columns to investigate the leaching of nitrate ( $ {\text{NO}}_3^{ - } $ ), ammonium ( $ {\text{NH}}_4^{ + } $ ), and nitrite ( $ {\text{NO}}_2^{ - } $ ) from calcareous soils that had received an average of 200?kg^?1 N?ha^?1?year^?1 for the previous 30?years and (2) to determine the relationship between soil properties and $ {\text{NO}}_3^{ - } $ , $ {\text{NH}}_4^{ + } $ , and $ {\text{NO}}_2^{ - } $ leaching. The soils used in this study ranged in texture from clay to sandy loam. Leaching experiments were conducted under saturation conditions and consisted of the collection of 1,047–2,524?mL of leachate (12 pore volumes (PVs)), which was equivalent to 534–1,286?mm from rainfall or irrigation. Losses of $ {\text{NO}}_3^{ - } $ ranged from 62 to 437?kg?ha^?1, while losses of $ {\text{NH}}_4^{ + } $ and $ {\text{NO}}_2^{ - } $ ranged from 2.5 to 19.3?kg?ha^?1 and 0.1 to 10.6?kg?ha^?1, respectively. Leaching rates differed between soil samples. The initial and secondary rate of $ {\text{NO}}_3^{ - } $ leaching was determined using an exponential model, and it ranged from 2.8 to 14.7?mg?kg^?1 PV^?1 and 0.11 to 0.32?mg?kg^?1 PV^?1. Greater leaching rates in the initial period could be due to leaching of $ {\text{NO}}_3^{ - } $ in solution, while the secondary leaching might be attributable to the diffusion-controlled transfer of $ {\text{NO}}_3^{ - } $ between mobile and immobile liquid phases. Analysis of variance indicated that the effects of soil type on total $ {\text{NO}}_3^{ - } $ leaching were highly significant (p?<?0.001). The results showed that soil $ {\text{NO}}_3^{ - } $ concentration was positively correlated with the peak concentration of $ {\text{NO}}_3^{ - } $ (r?=?0.86; p?<?0.01) and the total $ {\text{NO}}_3^{ - } $ leached (r?=?0.93; p?<?0.01). In addition, the total $ {\text{NH}}_4^{ + } $ leached was positively correlated with silt (r?=?0.67; p?<?0.05), clay (r?=?0.61; p?<?0.05), and pH (r?=?0.77; p?<?0.01), which suggests that soil parameters might be useful indicators of $ {\text{NO}}_3^{ - } $ and $ {\text{NH}}_4^{ + } $ leaching from calcareous soils. Nitrate leaching from soils could threaten groundwater supplies, so possible strategies for minimizing $ {\text{NO}}_3^{ - } $ leaching losses may need to be considered.     

Study of evaluation of groundwater in Gadilam basin using hydrogeochemical and isotope data

Gadilam river basin has gained its importance due to the presence of Neyveli Lignite open cast mines and other industrial complexes. It is also due to extensive depressurization of Cuddalore aquifer, and bore wells for New Veeranam Scheme are constructed downstream of the basin. Geochemical indicators of groundwater were used to identify the chemical processes that control hydrogeochemistry. Chemical parameters of groundwater such as pH, electrical conductivity, total dissolved solids, sodium (Na^?+?), potassium (K^?+?), calcium (Ca^?+?), magnesium (Mg^?+?), bicarbonate $({\rm HCO}_{3}^{-})$ , sulfate $({\rm SO}_{4}^{-})$ , phosphate $({\rm PO}_{4}^{-})$ , and silica (H₄SiO₄) were determined. Interpretation of hydrogeochemical data suggests that leaching of ions followed by weathering and anthropogenic impact controls the chemistry of the groundwater. Isotopic study reveals that recharge from meteoric source in sedimentary terrain and rock–water interaction with significant evaporation prevails in hard rock region.     

Ionic and heavy metal composition of respirable particulate in Madurai, India

Airborne particulate matter (PM₁₀) was collected for a period of 1 year at six locations in Madurai city, India. The chemical analyses on PM₁₀ samples were carried out for the estimation of heavy metals and ions using atomic absorption spectroscopy and ion chromatography respectively. The average PM₁₀ concentrations varied from 97.2 to 152.5 μg/m³, which were found to be below the Indian air quality standards. While industrial areas had the highest concentrations of heavy metals such as Fe, Zn and Cr and also the $\text{SO}_{4}^{2-}$ ions, traffic areas with relatively higher traffic densities in the city endured highest concentrations of Cd and the $\text{NO}_{3}^{-}$ ion. As gaseous pollutants serve as precursors of ionic particles in the atmospheric environment, gaseous pollution control is necessitated along with particulate with special reference to heavy metal and ion pollution abatement for the sustainable development of Madurai city.     

Acidic and basic properties and buffer capacity of airborne particulate matter in an urban area of Beijing

Particles with aerodynamic diameters <10  $\upmu $ m (PM₁₀) and particles with aerodynamic diameters <2.5  $\upmu $ m (PM_2.5) were sampled during summer 2006 in Beijing and mass concentrations, water-soluble ionic compounds concentrations, and acidic buffer capacity were analyzed. Results show that the mass concentration ranges of PM₁₀ and PM_2.5 were from 56.4 to 226.6  $\upmu $ g/m³ and from 31.3 to 200.7  $\upmu $ g/m³ during sampling days, respectively. Concentrations of F^???, Cl^???, NO $_{3}^{\,\,-}$ , NO $_{2}^{\,\,-}$ , SO $_{4}^{\,\,2-}$ , Ac^???, Ca^2?+?, Na^?+?, K^?+?, Mg^2?+?, and NH $_{4}^{\,\,+}$ in particles were analyzed by ion chromatography. Microtitration was adapted to determine the acidic?Cbasic property and the change of the buffering systems in different pH of the aqueous solution in which the PM is suspended. The major alkalinity and buffer capacity of particles were analyzed and calculated. The average carbonate buffer capacity was 0.3 mmol/g in PM_2.5 and 0.7 mmol/g in PM₁₀. The average acetic acid buffer capacity was 0.1 mmol/g in PM_2.5 and 0.3 mmol/g in PM₁₀. Carbonate and acetic acid are the main species for the buffer capacity in the particle phase. The average mass of carbonate was 71.0 mg/g in PM₁₀ and 46.7 mg/g in PM_2.5. The average mass of acetic acid was 11.2 mg/g in PM_2.5 and 20.0 mg/g in PM₁₀.     

Understanding and eliminating iron interference in colorimetric nitrate and nitrite analysis

Across many environments, nitrate ( $\mbox{NO}_{3}^-$ ) is an important form of N available for microorganisms and photosynthetic organisms. Accurate $\mbox{NO}_{3}^-$ measurements are important for examining N cycling and retention in terrestrial and aquatic ecosystems, but a common method of $\mbox{NO}_{3}^-$ analysis can underestimate $\mbox{NO}_{3}^-$ concentrations when soluble iron is present (iron > 10 mg L^???1). The basic method is robust, using copperized cadmium to reduce $\mbox{NO}_{3}^-$ and then diazotizing the resulting $\mbox{NO}_{2}^-$ in a two-step process to form an easily measured colored product. We show that iron interference is unique to using an NH₄Cl and ethylenediaminetetraacetic acid (EDTA) buffer. We hypothesize that interference is through iron-catalyzed reduction of the intermediate color product, a diazonium ion. We examine three historical buffers as alternatives to NH₄Cl/EDTA and recommend replacement of EDTA with diethylenetriaminepentaacetic acid, which chelates metals much like EDTA, but unlike EDTA, it does not cause interference in the presence of iron.     

Hydrogeochemical characterization of fluoride rich groundwater of Wailpalli watershed, Nalgonda District, Andhra Pradesh, India

The groundwater of Nalgonda district is well known for its very high fluoride content for the past five decades. Many researchers have contributed their scientific knowledge to unravel causes for fluoride enrichment of groundwater. In the present paper, an attempt has been made to relate the high fluoride content in the groundwater to hydrogeochemical characterization of the water in a fracture hard rock terrain—the Wailpally watershed. Groundwater samples collected from all the major geomorphic units in pre- and post-monsoon seasons were analyzed for its major ion constituents such as Ca^2?+?, Mg^2?+?, Na^?+?, K^?+?, CO $_{3}^{-}$ , HCO $_{3}^{-}$ , Cl^???, SO $_{4}^{-2}$ , NO $_{3}^{-}$ , and F^???. The groundwaters in the watershed have the average fluoride content of 2.79 mg/l in pre-monsoon and 2.83 mg/l in post-monsoon. Fluoride concentration in groundwater does not show perceptible change neither with time nor in space. The ionic dominance pattern is in the order of Na^?+? > Ca^2?+??> Mg^2?+??> K^??? among cations and HCO $_{3}^{-}\:\,>$ Cl^????> SO $_{4}^{-2} >$ NO $_{3}^{-} >$ F^??? among anions in pre-monsoon. In post-monsoon, Mg replaces Ca^2?+? and NO $_{3}^{-}$ takes the place of SO $_{4}^{-2}$ . The Modified Piper diagram reflect that the water belong to Ca^?+?2–Mg^?+?2–HCO $_{3}^{-}$ to Na^?+?–HCO $_{3}^{-}$ facies. Negative chloralkali indices in both the seasons prove that ion exchange between Na^?+? and K^?+? in aquatic solution took place with Ca^?+?2 and Mg^?+?2 of host rock. The interpretation of plots for different major ions and molar ratios suggest that weathering of silicate rocks and water–rock interaction is responsible for major ion chemistry of groundwater in Wailpally watershed. Chemical characteristics and evolution of this fluoride-contaminated groundwater is akin to normal waters of other hard rock terrain; hence, it can be concluded that aquifer material play an important role in the contribution of fluoride in to the accompanying water. High fluoride content in groundwater can be attributed to the continuous water–rock interaction during the process of percolation with fluorite-bearing country rocks under arid, low precipitation, and high evapotranspiration conditions.     

Assessment of dry season surface, ground, and treated water quality in the Cape Coast municipality of Ghana

This aim of this monitoring was to assess water quality in a dry season for the Cape Coast municipality in Ghana, which has been experiencing chronic water shortages. Fifteen different sampling stations—four surface, five ground, and six tap water samples—were analyzed for physicochemical and microbiological parameters during January to April 2005. Levels or trends in water quality that may be deleterious to sensitive water uses, including drinking, irrigation, and livestock watering have been noted with reference to well-established guidelines. Exceedances to some health-based drinking water guidelines included positive coliform for various water samples; pH for all groundwater samples (pH 5.9 ± 0.3); conductivity for 50% groundwater; color for about a third of groundwater and tap water; Mn for 44% tap water, 67% groundwater, and 50% surface water samples. The World Health Organization laundry staining Fe guideline of 0.3 mg/l was exceeded by 75% of surface water, 44% tap water, and 53% groundwater samples. The corresponding Mn guideline of 0.1 mg/l was exceeded by all the water samples. Respectively, all surface water samples and also 75% of the surface water exceeded some known Cu and Zn guideline for the protection of aquatic life. Compared to some historic data for Fosu Lagoon, the current study shows a lowering of ~1 pH unit, increase of ~65% $\text{NH}_{3}$ , one to two orders of magnitude increase in PO $_{4}^{{3}^{-}}$ , and more than two orders of magnitude increase in NO $_{3}^{-}$ . In several instances, tap water samples collected at the consumers’ end of the distribution system did not reflect on the true quality of the treated water. Mn, SO $_{4}^{{2}^{-}}$ , PO $_{4}^{{3}^{-}}$ , Cu, and Zn were among the chemical contaminations observed to occur in the distribution system.     

Groundwater geochemistry in the Alisadr, Hamadan, western Iran

The chemical composition of 59 well water samples throughout the Alisadr area, Hamadan, western Iran was determined in order to describe the background ion concentration and to identify the major hydrogeochemical processes that control the observed groundwater chemistry. The hydrochemical types, Ca–HCO₃, Ca–SO₄, dominate the largest part of the groundwater followed by water types Ca–Cl and Mg–HCO₃. Total hardness indicated that 30% of groundwater samples fell in the very hard water category. Ninety-seven percent of the water samples showed nitrate ( ${\rm NO}_{3}^{-})$ concentrations above the human affected value (13 mg l^???1 ${\rm NO}_{3}^{-})$ , while 15% exceeded the maximum acceptable level (50 mg l^???1 ${\rm NO}_{3}^{-})$ according to WHO regulations. With respect to sodium adsorption ratio, the groundwater can be used for irrigation on almost all soils with little danger of the developing harmful levels of exchangeable Na^?+?. But with respect to electrical conductivity, the water quality for irrigation was low to medium, providing the necessary drainage to avoid the buildup of toxic salt concentrations. Geochemical modeling using PHREEQC enabled prediction of the saturation state of minerals and indicated the dissolution and precipitation reactions occurring in the groundwater. Groundwaters were undersaturated with respect to amorphous silica. Stability diagram indicated that the dominant cluster of groundwater samples fell into the K-feldspar field.     

Determination of redox potential of sulfidic groundwater in unconsolidated sediments by long-term continuous in situ potentiometric measurements

This study was undertaken to investigate the redox potential (Eh) of sulfidic groundwater in unconsolidated sediments. The Eh was determined by long-term (several days to several weeks) continuous in situ potentiometric measurements using a platinum (Pt) electrode. The Eh values measured in two monitoring campaigns were ?259 and ?202 mV, respectively. Chemical analysis of groundwater showed that the redox species in the groundwater were sulfide (S^2???) and iron, respectively. The saturation indices calculated from the chemical analysis results indicated that FeS_(am) and mainly mackinawite were close to equilibrium in the analyzed waters. Comparison of the measured Eh values with those calculated using different redox couples revealed that the Eh values measured in the first monitoring campaign were nearly equal to those calculated using HS^???/SO $_{4}{^{2-}}$ , S^2???/SO $_{4}{^{2-}}$ , FeS $_{(\text{am})}$ /SO $_{4}{^{2-}}$ , and mackinawite/SO $_{4}{^{2-}}$ redox couples; on the other hand, the Eh values measured in the second monitoring campaign were almost consistent with those measured using the FeS₂/SO $_{4}{^{2-}}$ redox couple. The good fit between the measured Eh values and the theoretical calculated Eh values suggests that the sulfur system is related to the Eh value of sulfidic groundwater in unconsolidated sediments.     

Arsenic in shallow aquifer in the eastern region of Bangladesh: insights from principal component analysis of groundwater compositions

Probable sources and mechanisms of arsenic (As) release in shallow aquifer in eastern Bangladesh are evaluated using statistical analysis of groundwater compositions. Dissolved As in 39 samples ranged from 8.05 to 341.5 μg/L with an average of 95.14 μg/L. Ninety seven percent of wells exceed the WHO limit (10 μg/L) for safe drinking water. Principal component analysis is applied to reduce 16 measured compositional variables to five significant components (principal components—PCs) that explain 86.63% of the geochemical variance. Two component loadings, namely PC 1 and PC 2 (45.31% and 23.05%) indicate the natural processes within the aquifers in which organic matter is a key reactant in the weathering reactions. Four groups of wells are defined by the PCA and each group of wells represents distinct physicochemical characteristics. Among them, group III groundwater shows higher As concentration together with high concentrations of Fe, Mn, dissolved organic carbon, $\text{PO}_{4}^{3-}$ and $\text{HCO}_{3}^{-}$ than groups I and II. Speciation calculations suggest that only wells of group III are saturated with respect to siderite, and all groups of samples are supersaturated with respect of rhodochrosite. The relationship of As with these parameters in the different groups of wells of the study area suggests that reductive dissolution of Fe–Mn oxyhydroxides with microbially mediated degradation of organic matter is considered to be the dominant processes to release As in groundwater.     

Assessment of surface water quality of the Ceyhan River basin, Turkey

In this study, surface water quality of the Ceyhan River basin were assessed and examined with 13 physico-chemical parameters in 31 stations in 3 months during the period of 2005. Multivariate statistical techniques were applied to identify characteristics of the water quality in the studied stations. Nutrients, Cl^??? and Na^?+? affected mostly to the stations of Erkenez 2, S?r 2, and S?r 3 in the ordination diagram of correspondence analysis. Three factors were extracted by principal component analysis, which explains 79.14% of the total variation. The first factor (PC1) captures variables of EC, DO, NO $_{2}^{\; -}$ , PO $_{4}^{\; \equiv }$ , Cl^???, SO $_{4}^{\; =}$ , Na^?+?, and Ca^?+?+?. The second factor (PC2) is significantly related to pH, NH $_{3}^{\; -}$ , and Mg^?+?+?, while water temperature (T) and NO $_{3}^{\; -}$ accounted for the greatest loading for factor 3 (PC3). The stations were divided into three groups for PC1, two groups for PC2, and three groups for PC3 by hierarchical cluster analysis. The stations in the vicinity of cities presented low dissolved oxygen and high concentration of physico-chemical parameter levels. The stations of Erkenez 2, S?r 2, S?r 3, and Aksu 4 located near the city of Kahramanmara? were characterized by an extremely high pollution due to discharge of wastewater from industry and domestic. P?narba?? and Elbistan stations were also influenced by household wastewater of the city of Elbistan. According to criteria of Turkish Water Pollution Control Regulation, Erkenez 2, S?r 2, and S?r 3 stations have high polluted water. This study suggests that it is urgent to control point pollutions, and all wastewater should be purified before discharge to the Ceyhan River basin.     

Assessment of dissolved heavy metal in the Yangtze River estuary and its adjacent sea, China

The purpose of this paper is to determine the concentrations of dissolved heavy metals namely mercury (Hg), lead (Pb), cadmium (Cd), and copper (Cu) and to investigate the relationships between nutrients (nitrate-nitrogen and phosphate) and dissolved heavy metals. For this purpose, the concentrations of dissolved heavy metals were measured through 51 voyages form 1984 to 2006 in the Yangtze river estuary and its adjacent sea. Results analysis showed that dissolved heavy metals were not the main pollutants in the Yangtze river estuary, and the main source of heavy metal contamination was industrial wastewater from terrestrial pollution during the past 20 years. Heavy metal values showed significant abundance in the south branch of the Yangtze River estuary and Hangzhou Bay. In addition, Pb showed negative correlation with nutrients, while the positive correlations between Hg, Cd, and nutrients were shown. The obtained molar ratios, $\Delta \mbox{Cd}/\Delta \mbox{N} = 1.68 \times 10^{-5}$ and $\Delta \mbox{Cd}/\Delta \mbox{P} = 1.66 \times 10^{-4}$ , are close to those in plankton, showing the biogeochemical behavior and process of dissolved cadmium.     

Seasonal variation, source, and regional representativeness of the background aerosol from two remote sites in western China

Using observations from two remote sites during July 2004 to March 2005, we show that at Akdala (AKD, 47° 06′ N, 87° 58′ E, 562 m asl) in northern Xinjiang Province, there were high wintertime loadings of organic carbon (OC), elemental carbon (EC), and water-soluble (WS) ${\rm SO}_{4}^{2-}$ , ${\rm NO}_{3}^{2-}$ , and ${\rm NH}_{4}^{+}$ , which is similar to the general pattern in most areas of China and East Asia. However, at Zhuzhang (ZUZ, 28° 00′ N, 99° 43′ E, 3,583 m asl) in northwestern Yunnan Province, the aerosol concentrations and compositions showed little seasonal variation except for a decreasing trend of OC from August to autumn–winter. Additionally, the OC variations dominated the seasonal variation of PM₁₀ (particles ≤10 μm diameter) level. Chemical characteristics combined with transport information suggested sea salt origin of ionic Na^?+?, Mg^2?+?, and Cl^??? at ZUZ. At AKD, ionic Ca^2?+?, Mg^2?+?, Na^?+?, and Cl^??? primarily originated from salinized soil. Furthermore, the WS Ca^2?+? contributions (5.4–6%) to the PM₁₀ mass during autumn, winter, and early spring reflected a constant dust component. The results of this study indicated that both sites were regionally representative. However, the representative regions and scales of these background sites may vary seasonally as the regional atmospheric transport patterns change. Seasonal variations in the background aerosol levels from these two areas need to be considered when evaluating the regional climate effects of the aerosols.     

The hydrochemistry of groundwater in the Densu River Basin, Ghana

Hydrochemical analyses of groundwater samples were used to establish the hydrochemistry of groundwater in the Densu River Basin. The groundwater was weakly acidic, moderately mineralized, fresh to brackish with conductivity ranging from of 96.6 μS cm^???1 in the North to 10,070 μS cm^???1 in the South. Densu River basin have special economic significance, representing the countries greatest hydrostructure with freshwater. Chemical constituents are generally low in the North and high in the South. The order of relative abundance of major cations in the groundwater is Na^?+??> Ca^2?+??> Mg^2?+??> K^?+? while that of anions is Cl^????> HCO $_{3}^{-} >$ SO $_{4}^{2-} >$ NO $_{3}^{-}$ . Four main chemical water types were delineated in the Basin. These include Ca–Mg–HCO₃, Mg–Ca–Cl, Na–Cl, and mixed waters in which neither a particular cation nor anion dominates. Silicate weathering and ion exchange are probably the main processes through which major ions enter the groundwater system. Anthropogenic activities were found to have greatly impacted negatively on the quality of the groundwater.     

Hydrochemistry and evaluation of groundwater suitability for irrigation and drinking purposes in the Markandeya River basin, Belgaum District, Karnataka State, India

Markandeya River basin stretches geographically from 15°56?? to 16°08?? N latitude and 74°37?? to 74°58?? E longitude, positioned in the midst of Belgaum district, in the northern part of Karnataka. Since the quantity and quality of water available for irrigation in India is variable from place to place, groundwater quality in the Markandeya River basin was evaluated for its suitability for drinking and irrigation purposes by collecting 47 open and bore-well samples during the post-monsoon period of 2008. The quality assessment was made by estimating pH, electrical conductivity, total dissolved solids, hardness, and alkalinity besides major cations (Na^?+?, K^?+?, Ca^2?+?, and Mg^2?+?) and anions (HCO $_{3}^{\,\,-}$ , Cl^???, SO $_{4}^{\,\,2-}$ , PO $_{4}^{\,\,3-}$ , F^???, and NO $_{3}^{\,\,-}$ ). Based on these analyses, irrigation quality parameters like, sodium absorption ratio, %Na, residual sodium carbonate, residual sodium bicarbonate, chlorinity index, soluble sodium percentage, non-carbonate hardness, potential salinity, permeability index, Kelley??s ratio, magnesium hazard/ratio, index of base exchange, and exchangeable sodium ratio were calculated. According to Gibbs?? ratio, majority of water samples fall in the rock dominance field. The groundwater samples were categorized as normal chloride (95.75%), normal sulfate (95.75%), and normal bicarbonate (61.70%) water types based on Cl, SO₄, and HCO₃ concentrations. Based on the permeability index, majority of the samples belongs to classes 1 and 2, suggesting the suitability of groundwater for irrigation. The negative index of base exchange indicates the existence of chloro-alkaline disequilibrium (indirect base exchange reaction) existing in majority of the samples (68.08%) from the study area.