Wet atmospheric deposition of nitrogen: 20 years measurement in Shenzhen City, China

We presented measurements of wet deposition of NH ₄ ⁺ –N and NO ₃ ^? –N from 1986 to 2006 in Shenzhen City, China. Over the past 20 years, NO ₃ ^? –N concentration had significantly increased, but a reverse trend was found for NH ₄ ⁺ –N. The main form of total inorganic nitrogen (TIN) was NH ₄ ⁺ –N and the average NH ₄ ⁺ –N/NO ₃ ^? –N ratio was 1.57 in this area. The contribution of NO ₃ ^? –N to TIN increased from 28–42% in the period of 1986–2000 to 50–63% during 2001–2006. The increased deposition flux of NO ₃ ^? –N resulted in the increasing trend of TIN, although NH ₄ ⁺ –N showed a decreasing trend over time. Average deposition flux of TIN during 1986–2006 was 13.24 kg/ha/year, with a minimum value of 6.03kg/ha/year in 1988 and a maximum value of 20.52 kg/ha/year in 1997. Wet deposition fluxes of N appeared to vary with season, 81% occurred in the warm season (from April to September). The wet deposition of TIN to the Shenzhen Reservoir reached 8,902 kg in 2006, which contributed 9.95% of the total nonpoint pollution to the reservoir and will be increased in the future.     

Influences of urban wastewaters on the stream water quality: a case study from Gumushane Province, Turkey

Urban wastewater in Turkey is primarily discharged without treatment to marine environments, streams and rivers, and natural and artificial lakes. Since it has been well established that untreated effluent in multi-use waters can have acute and chronic impacts to both the environment and human health, it is important to evaluate the consequences of organic enrichment relative to the structure and function of aquatic environment. We investigated the impacts of untreated municipal wastewater discharge from the city of Gumushane in the Eastern Black Sea Region of Turkey on the surface water quality of the stream Harsit. Several key water-quality indicators were measured: chemical oxygen demand (COD), ammonium nitrogen (NH ₄ ⁺ –N), nitrite nitrogen (NO ₂ ^? –N), nitrate nitrogen (NO ₃ ^? –N), total Kjeldahl nitrogen (TKN), total nitrogen (TN), orthophosphate phosphorus (PO ₄ ^3? –P), methylene blue active substances (MBAS), water temperature (t), pH, dissolved oxygen (DO), and electrical conductivity (EC). The monitoring and sampling studies were conducted every 15 days from March 2009 to February 2010 at three longitudinally distributed stations. While t, pH, DO, and EC demonstrated relatively little variability over the course of the study, other parameters showed substantial temporal and spatial variations. The most dramatic differences were noted in COD, NH ₄ ⁺ –N, NO ₂ ^? –N, TKN, TN, PO ₄ ^3— P, and MBAS immediately downstream of the wastewater discharge. Concentration increases of 309 and 418 % for COD, 5,635 and 2,162 % for NH ₄ ⁺ –N, 2,225 and 674 % for NO ₂ ^? –N, 283 and 478 % for TKN, 208 and 213 % for PO ₄ ^3? –P, and 535 and 1,260 % for MBAS were observed in the summer and autumn, respectively. These changes were associated with greatly diminished seasonal stream flows. Based on NO ₂ ^? –N, TKN, PO ₄ ^3— P, and MBAS concentrations, it was concluded that Harsit stream water was correctly classified as polluted. The most telling parameter, however, was NH ₄ ⁺ –N, which indicated highly polluted waters in both the summer and autumn. The elevated concentrations of both P and N in the downstream segment of the stream triggered aggressive growth of submerged algae. This eutrophication of river systems is highly representative of many urban corridors and is symptomatic of ongoing organic enrichment that must be addressed through improved water treatment facilities.     

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.     

The evolution of the science of Bear Brook Watershed in Maine, USA

The Bear Brook Watershed in Maine (BBWM), USA is a paired watershed study with chemical manipulation of one watershed (West Bear = WB) while the other watershed (East Bear = EB) serves as a reference. Characterization of hydrology and chemical fluxes occurred in 1987–1989 and demonstrated the similarity of the ca. 10 ha adjacent forested watersheds. From 1989–2010, we have added 1,800 eq (NH₄)₂SO₄ ha^???1 y^???1 to WB. EB runoff has slowly acidified even as atmospheric deposition of SO $_{4}^{2-}$ has declined. EB acidification included decreasing pH, base cation concentrations, and alkalinity, and increasing inorganic Al concentration, as SO $_{4}^{2-}$ declined. Organic Al increased. WB has acidified more rapidly, including a 6-year period of increasing leaching of base cations, followed by a long-term decline of base cations, although still elevated over pretreatment values, as base saturation declined in the soils. Sulfate in WB has not increased to a new steady state because of increased anion adsorption accompanying soil acidification. Dissolved Al has increased dramatically in WB; increased export of particulate Al and P has accompanied the acidification in both watersheds, WB more than EB. Nitrogen retention in EB increased after 3 years of study, as did many watersheds in the northeastern USA. Nitrogen retention in WB still remains at over 80%, in spite of 20+ years of N addition. The 20-year chemical treatment with continuous measurements of critical variables in both watersheds has enabled the identification of decadal-scale processes, including ecosystem response to declining SO $_{4}^{-2}$ in ambient precipitation in EB and evolving mechanisms of treatment response in WB. The study has demonstrated soil mechanisms buffering pH, declines in soil base saturation, altered P biogeochemistry, unexpected mechanisms of storage of S, and continuous high retention of treatment N.     

Factors and sources influencing ionic composition of atmospheric condensate during winter season in lower troposphere over Delhi, India

Atmospheric condensate (AC) and rainwater samples were collected during 2010–2011 winter season from Delhi and characterized for major cations and anions. The observed order of abundance of cations and anions in AC samples was NH ₄ ⁺ ?>?Ca²⁺?>?Na⁺?>?K⁺?>?Mg²⁺ and HCO ₃ ^? ?>?SO ₄ ^2? ?>?Cl^??>?NO ₂ ^? ?>?NO ₃ ^? ?>?F^?, respectively. All samples were alkaline in nature and Σ _cation/Σ _anion ratio was found to be close to one. NH ₄ ⁺ emissions followed by Ca²⁺ and Mg²⁺ were largely responsible for neutralization of acidity caused by high NO _x and SO₂ emissions from vehicles and thermal power plants in the region. Interestingly, AC samples show low nitrate content compared with its precursor nitrite, which is commonly reversed in case of rainwater. It could be due to (1) slow light-mediated oxidation of HONO; (2) larger emission of NO₂ and temperature inversion conditions entrapping them; and (3) formation and dissociation of ammonium nitrite, which seems to be possible as both carry close correlation in our data set. Principal component analysis indicated three factors (marine mixed with biomass burning, anthropogenic and terrestrial, and carbonates) for all ionic species. Significantly higher sulfate/nitrate ratio indicates greater anthropogenic contributions in AC samples compared with rainwater. Compared with rainwater, AC samples show higher abundance of all ionic species except SO₄, NO₃, and Ca suggesting inclusion of these ions by wash out process during rain events. Ionic composition and related variations in AC and rainwater samples indicate that two represent different processes in time and space coordinates. AC represents the near-surface interaction whereas rainwater chemistry is indicative of regional patterns. AC could be a suitable way to understand atmospheric water interactions with gas and solid particle species in the lower atmosphere.     

Effects of land use types on surface water quality across an anthropogenic disturbance gradient in the upper reach of the Hun River, Northeast China

Surface water quality is vulnerable to pollution due to human activities. The upper reach of the Hun River is an important water source that supplies 52 % of the storage capacity of the Dahuofang Reservoir, the largest reservoir for drinking water in Northeast China, which is suffering from various human-induced changes in land use, including deforestation, reclamation/farming, urbanization and mine exploitation. To investigate the impacts of land use types on surface water quality across an anthropogenic disturbance gradient at a local scale, 11 physicochemical parameters (pH, dissolved oxygen [DO], turbidity, oxygen redox potential, conductivity, biochemical oxygen demand [BOD₅], chemical oxygen demand [COD], total nitrogen [TN], total phosphorus [TP], NO ₃ ^? -N, and NH ₄ ⁺ -N) of water from 12 sampling sites along the upper reach of the Hun River were monitored monthly during 2009–2010. The sampling sites were classified into four groups (natural, near-natural, more disturbed, and seriously disturbed). The water quality exhibited distinct spatial and temporal characteristics; conductivity, TN, and NO ₃ ^? -N were identified as key parameters indicating the water quality variance. The forest and farmland cover types played significant roles in determining the surface water quality during the low-flow, high-flow, and mean-flow periods based on the results of a stepwise linear regression. These results may provide incentive for the local government to consider sustainable land use practices for water conservation.     

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.     

Toxicity assessment of textile effluents treated by advanced oxidative process (UV/TiO2 and UV/TiO2/H2O2) in the species Artemia salina L.

Textile industry wastes raise a great concern due to their strong coloration and toxicity. The objective of the present work was to characterize the degradation and mineralization of textile effluents by advanced oxidative processes using either TiO₂ or TiO₂/H₂O₂ and to monitor the toxicity of the products formed during 6-h irradiation in relation to that of the in natura effluent. The results demonstrated that the TiO₂/H₂O₂ association was more efficient in the mineralization of textile effluents than TiO₂, with high mineralized ion concentrations (NH ₄ ⁺ , NO ₃ ^? , and SO ₄ ^2? ) and significantly decreased organic matter ratios (represented by the chemical oxygen demand and total organic carbon). The toxicity of the degradation products after 4-h irradiation to Artemia salina L. was not significant (below 10 %). However, the TiO₂/H₂O₂ association produced more toxicity under irradiation than the TiO₂ system, which was attributed to the increased presence of oxidants in the first group. Comparatively, the photogenerated products of both TiO₂ and the TiO₂/H₂O₂ association were less toxic than the in natura effluent.     

Specific absorption and backscattering coefficients of the main water constituents in Poyang Lake, China

Obtaining and analyzing the specific inherent optical properties (SIOPs) of water bodies is necessary for bio-optical model development and remote sensing-based water quality retrievals and, further, for related ecological studies of aquatic ecosystems. This study aimed to measure and analyze the specific absorption and backscattering coefficients of the main water constituents in Poyang Lake, China. The specific absorption and/or backscattering coefficients of the main water constituents at 85 sampling sites (47 in 2010 and 38 in 2011) were measured and analyzed as follows: (1) the concentrations of chlorophyll a (C _CHL), suspended particulate matter (C _SPM) (including suspended particulate inorganic matter (C _SPIM) and suspended particulate organic matter (C _SPOM)), and the absorption coefficients of total particulate (a _p), phytoplankton (a _ph), and non-pigment particulate (a _d) were measured in the laboratory; (2) the total backscattering coefficients at six wavelengths of 420, 442, 470, 510, 590, and 700 nm, including the contribution of pure water, were measured in the field with a HydroScat-6 backscattering sensor, and the backscattering coefficients without the contribution of pure water (b _b) were then derived by subtracting the backscattering coefficients of pure water from the total backscattering coefficients; (3) the specific absorption coefficients of total particulate ( $ a_{\mathrm{p}}^{ * } $ ), phytoplankton ( $ {a_{{\mathrm{ph}}}}^{ * } $ ), and non-pigment particulate ( $ a_{\mathrm{d}}^{ * } $ ) were calculated by dividing a _p, a _ph, and a _d by C _SPM, C _CHL, and C _SPIM, respectively, while the specific backscattering coefficients of total suspended particulate matter ( $ b_{\mathrm{b}}^{ * } $ ) were calculated by dividing b _b by C _SPM; and (4) the $ {a_{{\mathrm{ph}}}}^{ * } $ , $ a_{\mathrm{d}}^{ * } $ , $ a_{\mathrm{p}}^{ * } $ and $ b_{\mathrm{b}}^{ * } $ of the remaining samples (46 in 2010 and 36 in 2011) were visualized and analyzed, and their relations to C _CHL, C _SPIM or C _SPM were studied, respectively. The main results are summarized as follows: (1) the $ {a_{{\mathrm{ph}}}}^{ * } $ values at 440 nm were 0.0367–0.7203 m²?mg^?1 with a mean of 0.1623?±?0.1426 m²?mg^?1 in 2010 and 0.0319–0.7735 m²?mg^?1 with a mean of 0.3145?±?0.1961 m²?mg^?1 in 2011; there existed significant, negative, and moderate correlations between $ {a_{{\mathrm{ph}}}}^{ * } $ and C _CHL at 400–700 nm in 2010 and 2011 (p?<?0.05); (2) The $ a_{\mathrm{d}}^{ * } $ values at 440 nm were 0.0672–0.2043 m²?g^?1 with a mean of 0.1022?±?0.0326 m²?g^?1 in 2010 and 0.0559–0.1347 m²?g^?1 with a mean of 0.0953?±?0.0196 m²?g^?1 in 2011; there existed negative correlations between $ a_{\mathrm{d}}^{ * } $ and C _SPIM, while the correlations showed overall decreasing and increasing trends before and after around 575 nm with increasing wavelengths, respectively; (3) The $ a_{\mathrm{p}}^{ * } $ values at 440 nm were 0.0690–0.1929 m²?g^?1 with a mean of 0.1036?±?0.0298 m²?g^?1 in 2010 and 0.0571–0.1321 m²?g^?1 with a mean of 0.1014?±?0.0191 m²?g^?1 in 2011, and the negative correlations between $ a_{\mathrm{p}}^{ * } $ and C _SPM were found in both years; (4) The $ b_{\mathrm{b}}^{ * } $ at the six wavelengths generally decreased with increasing wavelengths, while the $ b_{\mathrm{b}}^{ * } $ values at 420 nm were lower than those at 442 nm for some samples; the correlation between $ b_{\mathrm{b}}^{ * } $ and C _SPM increased with increasing wavelength. Such results can only represent the SIOPs during the sampling time periods, and more measurements and analyses considering different seasons need to be carried out in the future to comprehensively understand the SIOPs of Poyang Lake.     

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.     

Industrial hygiene and toxicity studies in unorganized bone-based industrial units

A large variety of ornamental and decorative items are manufactured from bone waste by various unorganized sectors in India. An initial survey indicated that workers were exposed at various phases of final product. The subjects (12 industrial units) were tested for total suspended particulate matter (TSPM), particulate matter <10  $\upmu $ m (PM₁₀), and particulate matter <2.5  $\upmu $ m (PM_2.5). Prevalent levels of TSPM ranged between 2.90 and 5.89 mg m^???3. Respirable fractions of occupational dust as PM₁₀ and PM_2.5 were found in the range of 0.30?C2.08 and 0.26?C0.50 mg m^???3, respectively. Cytotoxicity study was conducted using hemolysis as a sensitive marker. In an in vitro study, rat RBCs were exposed to the concentration of 25?C1,000  $\upmu $ g/ml for 15?C120 min. A considerable variation was observed in the hemolytic activity of samples collected from different areas. At 500  $\upmu $ g/ml concentration, the hemolytic activity (12 h) was found to be in the range of 18?C25%. Due to limitation in sample mass of respirable fractions, only one concentration (100  $\upmu $ g/ml/2 h) was used for comparative study on hemolysis of RBCs caused by PM₁₀ and PM_2.5. Interestingly, the hemolytic activity was more at PM_2.5 than PM₁₀ and TSPM. These results suggest that the respirable particles are capable of reaching deep into the respiratory system. The finding is significant notably when there are no standards available in occupationally exposed populations. This is the first such study. Data could be of importance to policy makers and regulators.     

Seasonal variations of water column nutrients in the inner area of Ariake Bay, Japan: the role of muddy sediments

To investigate seasonal variations of nutrient distribution in the mudflat–shallow water system, we conducted field surveys once a month from August 2007 to July 2008 in the inner area of Ariake Bay (IAB), Japan. The NH₄ ⁺–N concentration of the water column increased in autumn because of the high NH₄ ⁺ release from the sediments, ranging from 850 to 3,001 μmol?m^?2?day^?1. The NO₃ ^?–N concentration was maximal in January, which was thought to be caused by NO₃ ^? release from the oxic sediments and by NO₃ ^? regeneration due to water column nitrification. The PO₄ ^3?–P concentration of the water column was high in summer–autumn due to the high PO₄ ^3? release from the reduced sediments, ranging from 22 to 164 μmol?m^?2?day^?1. We estimated the total amounts of DIN and PO₄ ^3?–P release (R _DIN and $ {R_{{\mathrm{P}{{\mathrm{O}}_4}}}} $ , respectively) from the muddy sediment area of the IAB. In summer–autumn, R _DIN and $ {R_{{\mathrm{P}{{\mathrm{O}}_4}}}} $ corresponded to about 47.7 % of DIN input and about 116.6 % of PO₄ ^3?–P input from the river, respectively. Thus, we concluded that the muddy sediments were an important source of nutrients for the water column of the IAB during summer–autumn. In addition, we found that phosphorus necessary for the growth of Porphyra (Porphyra yezoensis, Rhodophyceae) would be insufficient in the water column when phosphorus during the Porphyra aquaculture period is supplied only from the river. Therefore, the phosphorus release from the muddy sediments was thought to play an important role in the sustainable production of Porphyra in Ariake Bay.     

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.     

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.     

Groundwater hydrogeochemistry of Trikala municipality, central Greece

Sixty-four samples from the groundwater resources of Trikala municipality, central Greece, were collected during two periods (2006 and 2007) and analyzed for physico-chemical parameters (temperature, pH, specific electrical conductivity, and total dissolved solids), major ions (Ca²⁺, Cl^?, HCO ₃ ^? , K⁺, Mg²⁺, Na⁺, NO ₃ ^? , SO ₄ ^2? ), and several potentially toxic elements (Al, B, Ba, Br, Ca, Ce, Cl, Cr, Cu, Fe, K, La, Li, Mg, Mn, Mo, Na, Nd, Ni, P, Pb, Rb, S, Sc, Si, Sn, Sr, U, V, Y, Zn). European Council directives and USEPA guidelines were used to assess the water quality. The results indicate that all samples are fresh water, suitable for human consumption. All basic ions and physico-chemical parameters have average concentrations below their recommended optimum limits with the exception of electrical conductivity, for January 2007, and nitrate for October 2006 and January 2007 sampling periods. This exceedance is the result of dissolution of minerals such as calcite and dolomite that are present in the surrounding rocks and the application of fertilizers, respectively. Lead is the only element with an average value that exceeds the recommended EC guideline, while special attention should be paid to one borehole (T9) which has elevated NO ₃ ^? values which may pose a risk to human health.     

Assessment of anthropogenic influences on surface water quality in urban estuary, northern New Jersey: multivariate approach

Concentrations of selected heavy metals (Cd, Cr, Cu, Pb, Ni, Fe, and Zn), nutrients (NO ₃ ^? and NH₃), fecal coliform colonies, and other multiple physical–chemical parameters were measured seasonally from 12 locations in an urban New Jersey estuary between 1994 and 2008. Stepwise regression, principal component analysis, and cluster analysis were used to group water quality results and sampling locations, as well as to assess these data’s relationship to sewage treatment effluents and the distance to the mouth of the river. The BOD₅, NH₃, NO ₃ ^? and fecal coliform counts clustered as one group and positively correlated to the distances from treated effluent and the measures of magnitude at the discharge points. Dissolved solids and most metal species scored high along a single principal component axes and were significantly correlated with the proximity to the industrialized area. From these data, one can conclude that the effluent discharge has been a main source of anthropogenic input to the Hackensack River over the past 15 years. Therefore, the greatest improvement to water quality would come from eliminating the few remaining combined sewer overflows and improving the removal of nutrients from treated effluents before they are discharged into the creeks and river.     

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.     

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.     

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.     

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.