On‐line Solid Phase Extraction of Copper in Water Samples with Flow Injection Flame Atomic Absorption Spectrometry

An on‐line solid phase extraction method for the preconcentration and determination of Cu(II) by flame atomic absorption spectrometry has been described. The procedure is based on the retention of Cu(II) ions at pH 6.0 on a minicolumn packed with Amberlite XAD‐1180 resin impregnated with chrome azurol S. After preconcentration, Cu(II) ions adsorbed on the impregnated resin were eluted by 1 mol L^?1 HNO₃ solution. Several parameters, such as pH, type of eluent, flow rates of sample and eluent solutions, amount of resin were evaluated. At optimized conditions, for 3.5 min of preconcentration time, the system achieved a detection limit of 1.0 µg L^?1, and a relative standard deviation of 1.2% at 0.2 µg mL^?1 copper. An enrichment factor of 56‐fold was obtained with respect to the copper determination. The proposed method was successfully validated by the analysis of standard reference material (TMDA 54.4 lake water) and recovery studies. The method was applied to the preconcentration of Cu(II) in natural water samples.     

Separation and Preconcentration of Cobalt Using a New Schiff Base Derivative on Amberlite XAD‐7

In this study, a new solid‐phase extraction procedure has been developed for preconcentration and determination of Co ions in different water samples by flame atomic absorption spectrometry (FAAS). Cobalt was preconcentrated as N,N′‐bis(pyridine‐2‐yl‐methyl)benzene‐1,4‐diamine (Co‐BPMBDA) from sample solutions using a column containing Amberlite XAD‐7 and was determined. In order to achieve the best performance for the method, effects of several parameters such as pH, concentrations of ligand, sample flow rate, eluent, and matrix ions on the method efficiency were investigated. Under optimum conditions, the preconcentration factor was found to be 200 for 1000 mL waters samples. Detection limit based on the 3S_b criterion was calculated as 0.24 µg/L for 100 mL of sample solution and relative standard deviation was found to be 1.8%. The method was applied to determine the trace amounts of cobalt in water samples.     

Preparation,Characterization of a Novel Chelating Resin Functionalized with o‐Hydroxybenzamide and Its Application for Preconcentration of Trace Metal Ions

A stable extractor of metal ions was synthesized through azo linking of o‐hydroxybenzamide (HBAM) with Amberlite XAD‐4 (AXAD‐4) and was characterized by elemental analyses, IR spectral, and thermal studies. Its water regain value and hydrogen ion capacity were found to be 12.93 and 7.68 mmol g^?1, respectively. The optimum pH range (with the half‐loading time [min], t_1/2) for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were 2.0–4.0 (5.5), 2.0–4.0 (7.0), 2.0–4.0 (8.0), 4.0–6.0 (9.0), 4.0–6.0 (12.0), and 2.0–4.0 (15.0), respectively. Comparison of breakthrough and overall capacities of the metals ascertains the high degree of column utilization (>70%). The overall sorption capacities for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) ions were found to be 0.29, 0.22, 0.20, 0.16, 0.13, and 0.11 mmol g^?1 with the corresponding preconcentration factor of 400, 380, 380, 360, 320, and 320, respectively. The limit of preconcentration was in the range of 5.0–6.3 ng mL^?1. The detection limit for Cu(II), Cr(III), Ni(II), Co(II), Zn(II), and Pb(II) were found to be 0.39, 0.49, 0.42, 0.59, 0.71, and 1.10 ng mL^?1, respectively. The AXAD‐4‐HBAM has been successfully applied for the analysis of natural water, multivitamin formulation, infant milk substitute, hydrogenated oil, urine, and fish.     

Preconcentration by Coprecipitation of Copper and Nickel with Mo(VI)/Triazole Derivative System and Their Determinations by Flame Atomic Absorption Spectrometry in Food and Water Samples

A new separation and preconcentration technique based on coprecipitation of Cu(II) and Ni(II) ions by the aid of Mo(VI)/di‐tert‐butyl{methylenebis[5‐(chlorobenzyl)‐4H‐1,2,4‐triazol‐3,4‐diyl]}biscarbamate (BUMECTAC) precipitate has been established. The Mo(VI)/BUMECTAC precipitate was dissolved by concentrated HNO₃ and the solution was completed to 5.0 mL with distilled/deionized water. The levels of the analyte ions were determined by flame atomic absorption spectrometer. The effects of experimental conditions like HNO₃ concentration, amount of BUMECTAC and Mo(VI), sample volume, etc. and also the influences of some foreign ions were investigated in detail on the quantitative recoveries of analyte ions. The preconcentration factors were found to be 40 for Cu(II) and 100 for Ni(II) ions. The detection limits for Cu(II) and Ni(II) ions based on 3σ (N:10) were 0.43 and 0.70 µg L^?1, respectively. The relative standard deviations were found to be lower than 4.0% for both analyte ions. The accuracy of the method was checked by spiked/recovery tests and the analysis of two certified reference materials (Environment Canada TM‐25.3 and CRM‐SA‐C Sandy Soil C). The procedure was successfully applied to sea water and stream water as liquid samples and baby food as solid sample in order to determine the levels of Cu(II) and Ni(II) ions.     

Selective Separation and Preconcentration of Fe(III) and Zn(II) Ions by Solvent Extraction Using a New Triketone Reagent

A simple, rapid, and accurate method was developed for separation and preconcentration of trace levels of iron(III) and zinc(II) ions in environmental samples. Methyl‐2‐(4‐methoxy‐benzoyl)‐3‐(4‐methoxyphenyl)‐3‐oxopropanoylcarbamate (MMPC) has been proposed as a new complexing agent for Fe(III) and Zn(II) ions using solvent extraction prior to their determination by flame atomic absorption spectrometry (FAAS). Fe(III) and Zn(II) ions can be selectively separated from Fe(II), Pb(II), Co(II), Cu(II), Mn(II), Cr(III), Ni(II), Cd(II), Ag(I), Au(III), Pd(II), Cr(VI), and Al(III) ions in the solution by using the MMPC reagent. The analytical parameters such as pH, sample volume, shaking time, amount of MMPC reagent, volume of methyl isobutyl ketone (MIBK), effect of ionic strength, and type of back extractant were investigated. The recovery values for Fe(III) and Zn(II) ions were greater than 95% and the detection limits for Fe(III) and Zn(II) ions were 0.26 and 0.32 µg L^?1, respectively. The precision of the method as the relative standard deviation changed between 1.8 and 2.1%. Calibration curves have a determination coefficient (r²) of at least 0.997 or higher. The preconcentration factor was found to be 100. Accuracy of the method was checked by analyzing of a certified reference material and spiked samples. The developed method was applied to several matrices such as water, hair, and food samples.     

A Multi‐Element Ion‐Pair Extraction for Trace Metals Determination in Environmental Samples

A multi‐element ion‐pair extraction method was described for the preconcentration of Cd(II), Co(II), Cr(III), Cu(II), Fe(III), Mn(II), Ni(II), Pb(II), and Zn(II) ions in environmental samples prior to their determinations by flame atomic absorption spectrometry (FAAS). As an ion‐pair ligand 2‐(4‐methoxybenzoyl)‐N′‐benzylidene‐3‐(4‐methoxyphenyl)‐3‐oxo‐N‐phenyl‐propono hydrazide (MBMP) was used. Some analytical parameters such as pH of sample solution, amount of MBMP, shaking time, sample volume, and type of counter ion were investigated to establish optimum experimental conditions. No interferences due to major components and some metal ions of the samples were observed. The detection limits of the proposed method were found in the range of 0.33–0.9 µg L^?1 for the analyte ions. Recoveries were found to be higher than 95% and the relative standard deviation (RSD) was less than 4%. The accuracy of the procedure was estimated by analyzing the two certified reference materials, LGC6019 river water and RTC‐CRM044 soil. The developed method was applied to several matrices such as water, hair, and food samples.     

Coprecipitation with Cu(II)‐4‐(2‐Pyridylazo)‐resorcinol for Separation and Preconcentration of Fe(III) and Ni(II) in Water and Food Samples

The coprecipitation method is widely used for the preconcentration of trace metal ions prior to their determination by flame atomic absorption spectrometry (FAAS). A simple and sensitive method based on coprecipitation of Fe(III) and Ni(II) ions with Cu(II)‐4‐(2‐pyridylazo)‐resorcinol was developed. The analytical parameters including pH, amount of copper (II), amount of reagent, sample volume, etc., were examined. It was found that the metal ions studied were quantitatively coprecipitated in the pH range of 5.0–6.5. The detection limits (DL) (n = 10, 3s/b) were found to be 0.68 µg L^?1 for Fe(III) and 0.43 µg L^?1 for Ni(II) and the relative standard deviations (RSD) were ≤4.0%. The proposed method was validated by the analysis of three certified reference materials (TMDA 54.4 fortified lake water, SRM 1568a rice flour, and GBW07605 tea) and recovery tests. The method was successfully applied to sea water, lake water, and various food samples.     

Determination of Cu,Fe, and Ni in Spices after Preconcentration on Diaion‐HP 20 Resin as Their Zincon Complexes

In this work, a new separation–preconcentration method was developed for the determination of trace amounts of Cu(II), Ni(II), and Fe(III) by flame atomic absorption spectrometry (FAAS). Analytes were complexed by using zincon (2‐[2‐[alpha(2‐hydroxy‐5‐sulfophenylazo) benzylidene] hydrazino] benzoic acid sodium salt). The analyte ions were quantitatively adsorbed on a Diaion HP‐20 resin at pH 5. The retained metal ions on the resin were eluted by acetone. The analytical parameters such as pH of the sample, eluent type and volume, sample volume, and flow rates of the solution and the eluent were investigated. The influences of concomitant ions on the recoveries of the analytes were also examined. The instrumental detection limits for the analytes after application of the presented solid‐phase extraction procedure were in the range of 0.72–1.41 µg/L. The validation of the presented procedure was checked by analyzing certified reference material of SRM1515 Apple Leaves. The procedure was performed by analyzing some spice samples.     

Ionic Liquid Modified Resin for the Adsorptive Removal of Dibutyl Phthalate: Equilibrium,Kinetic, and Thermodynamic Studies

This study evaluated the adsorptive properties of dibutyl phthalate (DBP) on room temperature ionic liquid (RTIL) modified XAD‐4 resin. The modified RTIL‐XAD 4 sorbent was characterized by FTIR. Effect of varying experimental conditions such as pH, contact time, temperature, shaking speed, concentrations, and interfering species were investigated by batch adsorption experiments. Adsorption was found to be most favorable at pH 6 within 30 min. Experimental data were evaluated in terms of kinetic, equilibrium, and thermodynamic modeling. Kinetics of the sorption was found to follow pseudo second order rate equation whereas Freundlich and D–R isotherms were the most suitable models to explain sorption phenomenon. Thermodynamically sorption was endothermic, irreversible, and spontaneous in nature.     

Temporal trends of hydro‐climatic variables and runoff response to climatic variability and vegetation changes in the Yiluo River basin,China

The Yiluo River is the largest tributary for the middle and lower reaches of the Yellow River below Sanmenxia Dam. Changes of the hydrological processes in the Yiluo River basin, influenced by the climatic variability and human activities, can directly affect ecological integrity in the lower reach of the Yellow River. Understanding the impact of the climatic variability and human activities on the hydrological processes in the Yiluo River basin is especially important to maintain the ecosystem integrity and sustain the society development in the lower reach of the Yellow River basin. In this study, the temporal trends of annual precipitation, air temperature, reference evapotranspiration (ET₀) and runoff during 1961–2000 in the Yiluo River basin were explored by the Mann‐Kendall method (M‐K method), Yamamoto method and linear fitted model. The impacts of the climatic variability and vegetation changes on the annual runoff were discussed by the empirical model and simple water balance model and their contribution to change of annual runoff have been estimated. Results indicated that (i) significant upwards trend for air temperature and significant downwards trend both for precipitation and ET₀ were detected by the M‐K method at 95% confidence level. And the consistent trends were obtained by the linear fitted model; (ii) the abrupt change started from 1987 detected by the M‐K method and Yamamoto method, and so the annual runoff during 1961–2000 was divided into two periods: baseline period (1961–1986) and changeable period (1987–2000); and (iii) the vegetation changes were the main cause for change of annual runoff from baseline period to changeable period, and climatic variability contributed a little to the change of annual runoff of the Yiluo River. Copyright © 2009 John Wiley & Sons, Ltd.     

Study of the Interaction Mechanism in the Biosorption of Copper(II) Ions onto Posidonia oceanica and Peat

A systematic approach was used to characterize the biosorption of copper(II) onto two biosorbents, Posidonia oceanica and peat, focusing on the interaction mechanisms, the copper(II) sorption–desorption process and the thermal behavior of the biosorbents. Sorption isotherms at pH 4–6 were obtained and the experimental data were fitted to the Langmuir model with a maximum uptake (q_max) at pH 6 of 85.78 and 49.69 mg g^?1, for P. oceanica and peat, respectively. A sequential desorption (SD) with water, Ca(NO₃)₂, and EDTA was applied to copper‐saturated biosorbents. Around 65–70% copper(II) were desorbed with EDTA, indicating that this heavy metal was strongly bound. The reversibility of copper(II) sorption was obtained by desorption with HCl and SD. Fourier transform IR spectroscopy (FTIR) analysis detected the presence of peaks associated with OH groups in aromatic and aliphatic structures, CH, CH₂, and CH₃ in aliphatic structures, COO^? and COOH groups and unsaturated aromatic structures on the surface of both biosorbents, as well as peaks corresponding to Si? O groups on the surface of peat. The results of SEM‐EDX and FTIR analysis of copper‐saturated samples demonstrated that ion exchange was one of the mechanisms involved in copper(II) retention. Thermal analysis of biosorbent samples showed that copper(II) sorption–desorption processes affected the thermal stability of the biosorbents.     

Nested‐Scale Nutrient Flux in a Mixed‐Land‐Use Urbanizing Watershed

To improve quantitative understanding of mixed‐land‐use impacts on nutrient yields, a nested‐scale experimental watershed study design (n = 5) was applied in a 303(d), clean water act impaired urbanizing watershed of the lower Missouri River Basin, USA. From 2010 to 2013, water samples (n = 858 sample days per site) were analysed for total inorganic nitrogen (TIN‐N), nitrite (NO₂–N) nitrate (NO₃–N), ammonia (NH₃–N), and total phosphorus (TP‐P). Annual, seasonal, and monthly flow‐weighted concentrations (FWCs) and nutrient yields were estimated. Mean nutrient concentrations were highest where agricultural land use comprised 58% of the drainage area (NH₃ = 0.111 mg/l; NO₂ = 0.045 mg/l; NO₃ = 0.684 mg/l, TIN = 0.840 mg/l; TP = 0.127 mg/l). Average TP‐P increased by 15% with 20% increased urban land use area. Highly variable annual precipitation was observed during the study with highest nutrient yields during 2010 (record setting wet year) and lowest nutrient yields during 2012 (extreme drought year). Annual TIN‐N and TP‐P yields exceeded 10.3 and 2.04 kg ha^?1 yr^?1 from the agricultural dominated headwaters. Mean annual NH₃–N, NO₂–N, NO₃–N, TIN‐N, and TP‐P yields were 0.742, 0.400, 4.24, 5.38, and 0.979 kg ha^?1 yr^?1, respectively near the watershed outlet. Precipitation accounted for the majority of the explained variance in nutrient yields (R² values from 0.68 to 0.85). Nutrient yields were also dependent on annual precipitation of the preceding year (R² values from 0.87 to 0.91) thus enforcing the great complexity of variable mixed‐land‐use mediated source‐sink nutrient yield relationships. Study results better inform land managers and best management practices designed to mitigate nutrient pollution issues in mixed‐land‐use freshwater ecosystems. Copyright © 2015 John Wiley & Sons, Ltd.     

Removal of Carbamazepine,Naproxen, and Trimethoprim from Water by Amberlite XAD‐7: A Kinetic Study

The adsorption kinetics of carbamazepine, naproxen, and trimethoprim in aqueous solution by Amberlite? XAD‐7 has been studied. The influence of adsorbent dose (1–3 g/L), stirring rate (80–240 rpm), pH (2–9), temperature (20–60°C), and initial concentration (25–75 ppm) on the adsorption kinetics has been analyzed. The removal efficiency in the first 2 h reaches 85% for carbamazepine, 60% for naproxen, and 70% for trimethoprim. pH appears to be the most important factor conditioning the removal of these latter solutes, whereas carbamazepine adsorption seems to be independent of the pH of the adsorptive solution. Initial concentration and operation temperature moderately influence the adsorption process. Finally, stirring rate scarcely affects the process. The experimental data have been fitted to four kinetic models, namely pseudo‐first and pseudo‐second order, intra‐particle diffusion and Bangham's. The model providing the best fit is the pseudo‐second order one. Again, pH is the factor that affects the adsorption rate in a more remarkable manner although other parameters such as temperature and stirring rate also contribute to accelerate the removal of the solutes. Under the optimal operation conditions, Amberlite? XAD‐7 exhibits a promising ability for the removal of the pharmaceuticals under study.     

Adsorption of Cadmium from Aqueous Solution by Ficus religiosa Leaf Powder and Characterization of Loaded Biosorbent

The present investigation evaluates the adsorption effectiveness of Cd(II) ions on Ficus religiosa leaf powder (FRL). The experimental parameters chosen included time, pH, particle size, temperature, adsorbate, anion, and Pb(II) concentrations. The time data followed pseudo‐second‐order kinetics. Cd(II) adsorption increased from 1.38 to 75.17% with the increase in pH from 2 to 4 and further increase in pH to 5.5 resulted in its marginal increase to 77.52%. Based on regression coefficient values, the isothermic data fitted the various models in the order Langmuir > Redlich–Peterson > Temkin > Freundlich model. The maximum loading capacity of FRL was estimated to be 27.14 mg g^?1. The presence of Cl^?, , or Pb²⁺ exhibited adverse effect on Cd(II) uptake. The thermodynamic parameters of enthalpy (ΔH⁰) and entropy (ΔS⁰) were estimated to be 8.31 kJ mol^?1 and 38.22 J mol^?1 K^?1, respectively. SEM‐EPMA of the loaded FRL showed Cd(II) distribution at specific sites. The XRD patterns of Cd(II) loaded FRL sample showed disappearance of some peaks corresponding to β‐Ca(PO₃)₂; shifting of peaks and decrease in %RI corresponding to γ‐CaSO₄ phase. Positive shift of IR bands for the Cd(II) loaded sample was observed.     

Comparison of methods for applying the Priestley–Taylor equation at a regional scale

The scenario assumed for this study was that of a region with a complete or first‐order weather station surrounded by a network of second‐order stations, where only monthly air temperature data were available. The objective was to evaluate procedures to estimate the monthly α parameter of the Priestley–Taylor equation in the second‐order stations by adjusting and extrapolating α values determined at the first‐order station. These procedures were applied in two climatic zones of north‐east Spain with semi‐arid continental and semi‐arid Mediterranean climates, respectively. Procedure A assumed α to be constant over each zone for each month (direct extrapolation). Procedure B accounted for differences in vapour pressure deficit and available energy for evapotranspiration between the first‐ and second‐order stations. Procedure C was based on equating the Penman–Monteith (P–M) and Priestley–Taylor (P–T) equations on a monthly basis to solve for α. Methods to estimate monthly mean vapour pressure deficit, net radiation and wind speed were developed and evaluated. A total of 11 automated first‐order weather stations with a minimum period of record of 6 years (ranging from 6 to 10 years) were used for this study. Six of these stations were located in the continental zone and five in the Mediterranean zone. One station in each zone was assumed to be first‐order whereas the remainder were taken as second‐order stations. Monthly α parameters were calibrated using P–M reference crop evapotranspiration (ET₀) values, calculated hourly and integrated for monthly periods, which were taken as ‘true’ values of ET₀. For the extrapolation of monthly α parameters, procedure A was found to perform slightly better than procedure B in the Mediterranean zone. The opposite was true in the continental zone. Procedure C had the worst performance owing to the non‐linearity of the P–M equation and errors in the estimation of monthly available energy, vapour pressure deficit and wind speed. Procedures A and B are simpler and performed better. Overall, monthly P–T ET₀ estimates using extrapolated α parameters and R_n?G values were in a reasonable agreement with P–M ET₀ calculated on an hourly basis and integrated for monthly periods. The methods presented for the spatial extrapolation of monthly available energy, vapour pressure deficit and wind speed from first‐ to second‐order stations could be useful for other applications. Copyright © 2001 John Wiley & Sons, Ltd.     

Adsorption Kinetic and Equilibrium Studies on Removal of Lead(II) onto Glutamic Acid/Sepiolite

In this study, a modified method was used to increase the adsorption of lead ions from aqueous solutions by using modified clay mineral on the laboratory scale. Adsorption experiments have been carried out on the use of both thermal activated sepiolite (TAS) and their glutamate/sepiolite modification (GS) as adsorbents. The experimental data was analyzed using adsorption kinetic models (pseudo first‐ and second‐order equations). The pseudo second‐order kinetic model fitted well to the kinetic data (R² ≥ 0.99). Then, the Freundlich and Langmuir models were applied to describe the uptake of Pb(II) on GS and the Langmuir isotherm model agrees well with the equilibrium experimental data (R² ≥ 0.97). The maximum adsorption capacity was observed to be 128.205 mg/g by GS according to the Langmuir equation. Desorption efficiency of the GS was studied by the batch method using EDTA, HCl, and HNO₃ solutions. Desorption of 69.18, 74.55, and 80% of Pb(II) from GS was achieved with 0.1 M EDTA, 0.1 M HCl, and 0.1 M HNO₃ solutions, respectively. FTIR analysis suggests the importance of functional groups such as amino, hydroxyl, and carboxyl during Pb(II) removal. SEM observations demonstrated that an important interaction at the lead‐modified sepiolite interface occurred during the adsorption process. In addition, the thermodynamic constants was calculated that the values of the Gibbs free energy (ΔG*), enthalpy (ΔH*), and entropy (ΔS*) of modification were 86.79 kJ/mol, ?18.91 kJ/mol, and ?354.70 J/mol/K, respectively. The negative value of ΔH* shows exothermic nature of adsorption.     

Fluorescence as a Tool for Tracing the Organic Contamination from Pulp Mill Effluents in Surface Waters

Three‐dimensional fluorescence spectra of water samples from an eucalyptus bleached kraft pulp mill and from a river, upstream and downstream of the discharge of the effluent, revealed the existence of a peak at δ_exc = 280 nm and δ_em = 340 nm Δδ = 60 nm), characteristic of effluentπs organic matter. Humic substances were isolated from the effluent by sequential adsorption onto resins XAD‐8 and XAD‐4 in series. Their synchronous fluorescence spectra with Δδ = 60 nm do also exhibit an intense signal at δ_exc = 280 nm (≈ 300 nm in the humic acid fraction). The peak is absent in the spectra of humic substances isolated from a non‐polluted site of the river, but it is clearly seen in the spectra of the humic substances from a site downstream of the discharge of the effluent. Synchronous fluorescence spectra (Δδ = 60 nm) of water samples from the river and its lagoon were recorded and revealed to be an easy and fast way of tracing the organic contamination from the effluent.     

Flame Atomic Absorption Spectrometry Determination of Trace Amounts of Cadmium and Zinc in Water Samples after Preconcentration onto Modified Amberlite XAD‐4 Resin

In the present article, a procedure for the simultaneous separation and preconcentration of trace amounts of cadmium and zinc is proposed. It is based on the adsorption of cadmium and zinc ions onto a column of Amberlite XAD‐4 resin loaded with aluminon reagent. Cadmium and zinc ions are quantitatively retained on the column in the pH range from 6.5–7.5, at a flow rate of 2 mL min^–1. The cadmium and zinc ions are eluted with 5.0 mL of 5 mol L^–1 HNO₃ solution. Cadmium and zinc are measured by flame atomic absorption spectrometry (FAAS). In the present case, 0.1 μg of cadmium and 0.5 μg of zinc can be concentrated in the column from 1000 mL of aqueous sample, where their concentrations are as low as 0.1 and 0.5 ng mL^–1, respectively. The relative standard deviations, for seven replicated determinations of 1.0 μg mL^–1 of cadmium and zinc, are 1.2 and 1.1%, respectively. The detection limits for cadmium and zinc in the original solution are 0.02 and 0.11 ng mL^–1, respectively. The interference of a large number of anions and cations has been studied and the optimized conditions are utilized for the determination of trace amounts of cadmium and zinc in different environmental and standard samples.     

Lithological and hydrological controls on water composition: evaporite dissolution and glacial weathering in the south central Andes of Argentina (33°–34°S)

Lithological and hydrological influence on fluvial physical and chemical erosion was studied in a glacierized sedimentary basin with high evaporite presence. Suspended particulate matter (SPM), total dissolved solids (TDS) and major ion concentrations were analysed for 2 years of different hydrologic condition: (i) 2009–2010, Q = 100% average; and (ii) 2010–2011, Q = 60% average. Annual hydrograph was simple regime‐type with one peak in summer related to snow melting. The intra‐annual SPM and TDS variations were directly and inversely associated to Q, respectively. Snow chemistry showed continental influence (Na⁺/Ca²⁺ = 0.17), and atmospheric input of TDS was <1% of the total exported flux. River water was highly concentrated in Ca²⁺ and SO₄²⁻ (~4 mmol l⁻¹) and in Na⁺ and Cl⁻ (~3 mmol l⁻¹). Ca²⁺/SO₄²⁻ and Na⁺/Cl⁻ molar ratios were ~1 and related to Q, directly and inversely, respectively. Major ion relationships suggest that river chemistry is controlled by evaporite (gypsum and halite) dissolution having a summer input from sulfide oxidation and carbonate dissolution, and a winter input from subsurface flow loaded with silicate weathering products. This variation pattern resulted in nearly chemostatic behaviour for Ca⁺, Mg²⁺ and SO₄²⁻, whereas Na⁺, Cl⁻ and SiO₂ concentrations showed to be controlled by dilution/concentration processes. During the 2009–2010 hydrological year, the fluxes of water, SPM and TDS registered in the snow melting–high Q season were, respectively, 71%, 92% and 67% of the annual total, whereas for equal period in 2010–2011, 56% of water, 86% of SPM and 54% of TDS annual fluxes were registered. The SPM fluxes for 2009–2010 and 2010–2011 were 1.19 × 10⁶ and 0.79 × 10⁶ t year⁻¹, whereas TDS fluxes were 0.68 × 10⁶ and 0.55 × 10⁶ t year⁻¹, respectively. Export rates for 2009–2010 were 484 t km² year⁻¹ for SPM and 275 t km² year⁻¹ for TDS. These rates are higher than those observed in glacierized granite basins and in non‐glacierized evaporite basins, suggesting a synergistic effect of lithology and glaciers on physical and chemical erosion. Copyright © 2014 John Wiley & Sons, Ltd.     

Hydrological responses to defoliation and drought of an upland oak/pine forest

Hydrologic variability during 2005–2011 was observed and analyzed at an upland oak/pine forest in the New Jersey Pinelands. The forest experienced defoliation by Gypsy moth (Lymantria dispar L.) in 2007, drought conditions in 2006 and a more severe drought in 2010. By using sap flux and eddy covariance measurements, stream discharge data from USGS, soil water changes, precipitation (P) and precipitation throughfall, a local water balance was derived. Average annual canopy transpiration (E_C) during 2005–2011 was 201 mm a^?1 ± 47 mm a^?1. A defoliation event reduced E_C by 20% in 2007 compared with the 2005–2011 mean. During drought years in 2006 and 2010, stand transpiration was reduced by 8% in July 2006 and by 18% in 2010, respectively, compared with the overall July average. During July 2007, after the defoliation and subsequent reflushing of half of the leaves, E_C was reduced by 25%. This stand may experience higher sensitivity to drought when recovering from a defoliation event as evidenced by the higher reduction of E_C in 2010 (post‐defoliation) compared with 2006 (pre‐defoliation). Stream water discharge was normalized to the watershed area by dividing outflow with the watershed area. It showed the greatest correlation with transpiration for time lags of 24 days and 219 days, suggesting hydrological connectivity on the watershed scale; stream water discharge increases when transpiration decreases, coinciding with leaf‐on and leaf‐off conditions. Thus, any changes in transpiration or precipitation will also alter stream water discharge and therefore water availability. Under future climate change, frequency and intensity of precipitation and episodic defoliation events may alter local water balance components in this upland oak/pine forest. Copyright © 2013 John Wiley & Sons, Ltd.