Assessment of physico-chemical qualities and heavy metal concentrations of Umgeni and Umdloti Rivers in Durban,South Africa

We assessed the effects of seasonal dynamics on the physico-chemical qualities and heavy metals concentrations of the Umgeni and Umdloti Rivers in Durban, South Africa. Water samples were taken from nine different sampling points and analysed for the following parameters; temperature, pH, turbidity, electrical conductivity (EC), biological oxygen demand (BOD₅), chemical oxygen demand (COD), phosphate (PO₄ ^2?), nitrate (NO₃ ^2?), ammonium (NH₄ ⁺), sulphate (SO₄ ^2?), lead (Pb²⁺), mercury (Hg²⁺), cadmium (Cd²⁺), aluminium (Al³⁺), and copper (Cu²⁺) using standard methods. The data showed variations it terms of the seasonal fluctuations and sampling regime as follows: temperature 12–26.5 °C; pH 5.96–8.45; turbidity 0.53–18.8 NTU; EC 15.8–5180 mS m^?1; BOD₅ 0.60–7.32 mg L^?1; COD 10.5–72.9 mg L^?1; PO₄ ^2??<?500–2,460 μg L^?1; NO₃ ^2? <0.05–4.21 mg L^?1; NH₄ ⁺?<?0.5–1.22 mg L^?1; SO₄ ^2? 3.90–2,762 mg L^?1; Pb²⁺ 0.023–0.135 mg L^?1; Hg²⁺ 0.0122–0.1231 mg L^?1 Cd²⁺ 0.068–0.416 mg L^?1; Al³⁺ 0.037–1.875 mg L^?1, and Cu²⁺0.006–0.144 mg L^?1. The concentrations of most of the investigated parameters exceeded the recommended limit of the South African Guidelines and World Health Organization tolerance limits for freshwater quality. We conclude that these water bodies are potentially hazardous to public health and this highlights the need for implementation of improved management strategies of these river catchments for continued sustainability.     

A field study of the relationship between sulfide-bound metals and bioaccumulation by Limnodrilus sp. in a heavily polluted river

Acid volatile sulfide (AVS) has been regarded as an important factor controlling metal bioavailability in anoxic sediments, but its effect on metal accumulation under natural conditions is poorly understood. Here, a field study of the influence of AVS on metal accumulation by Limnodrilus sp. in a heavily polluted river is provided. Most of the study area was subject to anaerobic and strongly reducing conditions, and the concentration of trace metals in surface sediments was high, as were the concentration of AVS and simultaneously extracted metals (SEM; average AVS?=?20.3 μmol g^?1, average ∑SEM₅?=?9.42 μmol g^?1; ∑SEM₅ refers to the sum of SEM_Cd, SEM_Cu, SEM_Pb, SEM_Ni, and SEM_Zn). Only a few species and small quantities of benthic invertebrates were found, and Limnodrilus sp. was dominant. There was no correlation between trace metal accumulation and (SEM-AVS), and in stations where (SEM-AVS) <0, the absolute value of bioaccumulation was high (average ∑BIO₅?=?4.07 μmol g^?1; ∑BIO₅ refers to the sum of BIO_Cd, BIO_Cu, BIO_Pb, BIO_Ni, and BIO_Zn), indicating that there was no relationship between (SEM–AVS) and metal accumulation in Limnodrilus sp. This was likely because Limnodrilus sp. ingest sediment particles as their main food source, so pore water metals play a minor role in their bioaccumulation (BIO) of materials. However, ∑BIO₅ was significantly correlated with ∑SEM₅ (r?=?0.795, p?<?0.01), revealing that the large number of sulfide-bound metals (SEM) in sediments may play an important role in metal accumulation in Limnodrilus sp., which can assimilate sulfide-associated metals by the help of the digestive fluids in the digestive systems.     

FIA-coupled spectrophotometric method for determination of Cr (VI) traces in natural waters: application of in-line dissolution of 1,5-diphenylcarbazide after heat treatment and activated alumina as adsorbent for preconcentration

This work proposes the quantification of Cr (VI) ions in natural waters in trace level, using activated alumina (Al₂O₃) as preconcentration support, controlled in-line dissolution of the solidified chromophore diphenylcarbazide after heat treatment and spectrophotometric detection. The manifold ensures high sensitivity of analytical response, good repeatability, and stability. In this work, optimization of experimental conditions of a flow injection system was chosen as the parameters for greater sensitivity and better selectivity. The selected optimized conditions were 0.30 mol L^?1 for H₂SO₄ concentration, system flow rate as 0.40 mL min^?1, sample injection volume of 192.50 μL, 2 min for preconcentration time, and 0.10 mol L^?1 for eluent concentration. The analytical curves obtained for real sample analysis show linear range from 0.192 to 0.961 μM, linear correlation coefficient R?=?0.9997 and LOD?=?0.024 μM. The preconcentration factor of about four times was obtained through the passage of 800 μL of a standard solution containing 0.961 μM of Cr (VI) through mini-column of preconcentration followed by elution at 192.5 μL of NH₄OH 0.1 mol L^?1 solution. The solid chromogenic reagent presented high durability (weeks in daily use with mass of 0.0993 g) and good reproducibility in analytical signal. The reactivation of the mini-column of alumina should be executed after ten injections of eluent, using 800 μL of HCl 0.02 mol L^?1 solution in flow through the same. Each cycle of injection and elution of the sample takes about 5 min on the proposed terms. Despite the length of each cycle still be high, low concentrations can be detected using a technique of relatively low cost. This is due in part, the association dissolution of the chromogenic reagent directly in the line and the preconcentration step. Another important factor is the economy of reagent chromogenic, low generation of reject contributing to better quality of the environment, and the high potential for applications to work in field.     

Application of cold-induced aggregation microextraction as a fast,simple, and organic solvent-free method for the separation and preconcentration of Se(IV) in rice and various water samples

The developed method is based on cold-induced aggregation microextraction of Se(IV) using the 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid as an extractant followed by spectrophotometry determination. The extraction of Se(IV) was performed in the presence of dithizone as the complexing agent. In this method, a very small amount of 1-butyl-3-methylimidazolium hexafluorophosphate was added to the sample solution containing Se-dithizone complex. Then, the solution was kept in a thermostated bath at 50 °C for 4 min. Subsequently, the solution was cooled in an ice bath and a cloudy solution was formed. After centrifuging, the extractant phase was analyzed using a spectrophotometric detection method. Some important parameters that might affect the extraction efficiency were optimized (HCl, 0.6 mol L^?1; dithizone, 4.0?×?10^?6 mol L^?1; ionic liquid, 100 μL). Under the optimum conditions, good linear relationship, sensitivity, and reproducibility were obtained. The limit of detection (LOD) (3S_b/m) was 1.5 μg L^?1, and the relative standard deviation (RSD) was 1.2 % for 30 μg L^?1 of Se(IV). The linear range was obtained in the range of 5–60 μg L^?1. It was satisfactory to analyze rice and various water samples.     

Vehicular stress a cause for heavy metal accumulation and change in physico-chemical characteristics of road side soils in Pahalgam

In an effort to determine vehicular impact on soil quality, soil samples were collected from three different zones (Pahalgam, Batakote, and Chandanwari) in Pahalgam forest ecosystem. Results showed that a significant decrease in moisture content, organic carbon, available nitrogen, and potassium was observed in nearby road side soils. However, pH was observed to be on neutral side and available phosphorus recorded high concentration. The concentration of heavy metals Pb²⁺, Cu²⁺, Zn²⁺, Ni²⁺, and Cd²⁺ estimated was also significantly high. Furthermore, concentration of Pb²⁺ at high vehicular load subzones was observed to be highest (1.168 mg/Kg) followed by Zn²⁺ (0.896 mg/Kg), Ni²⁺ (0.649 mg/Kg), Cu²⁺ (0.415 mg/Kg), and Cd²⁺ (0.079 mg/Kg). An inter-zone analysis revealed that the concentration of the heavy metals (Pb²⁺?>?Ni²⁺?>?Cd²⁺) was observed to follow the trend, Z-I?>?Z-II?>?Z-III. Variation along the temporal gradient and the impact on soil qualities were notably higher in summer. Vehicular pollution to a great extent impacts physico-chemical characteristics and more interestingly adds substantial concentration of heavy metals in soils.     

Multiple metal tolerance and biosorption of cadmium by Candida tropicalis isolated from industrial effluents: glutathione as detoxifying agent

The ability of cadmium uptake by metal-resistant yeast, Candida tropicalis, from the liquid medium and wastewater was evaluated. The minimum inhibitory concentration of Cd^2?+? against C. tropicalis was 2,500 mg L^???1. The yeast also showed tolerance toward Zn^2?+? (1,400 mg L^???1), Ni^2?+? (1,000 mg L^???1), Hg^2?+? (1,400 mg L^???1), Cu^2?+? (1,000 mg L^???1), Cr^6?+? (1,200 mg L^???1), and Pb^2?+? (1,000 mg L^???1). The yeast isolate showed typical growth curves, but lag and log phases extended in the presence of cadmium. The yeast isolate showed optimum growth at 30°C and pH 8. The metal processing ability of the isolate was determined in a medium containing 100 mg L^???1 of Cd^2?+?. C. tropicalis could decline Cd^2?+? 70%, 85%, and 92% from the medium after 48, 96, and 144 h, respectively. C. tropicalis was also able to remove Cd^2?+? 40% and 78% from the wastewater after 6 and 12 days, respectively. Cd produced an increase in glutathione (GSH) and nonprotein thiol levels by 135% and 134% at 100-mg L^???1 concentration, respectively. An increase in the synthesis of GSH is involved in metal tolerance, and the presence of increasing GSH concentrations may be a marker for high metal stress in C. tropicalis. C. tropicalis, which is resistant to heavy metal ions and is adaptable to the local environmental conditions, may be employed for metal detoxification operations.     

Biogeochemical responses to nutrient inputs in a Cuban coastal lagoon: runoff, anthropogenic, and groundwater sources

Laguna Larga, a coastal lagoon in central Cuba, has been heavily altered by tourism infrastructure construction and sewage disposal. We hypothesize that this has decreased the circulation and caused eutrophication of the lagoon. To assess this, 12 bimonthly samplings were carried out in 2007–2008. Temperature, salinity, oxygen, nutrients and nitrogen, and phosphorous fractions (inorganic, organic, and total) were determined. Water and salt budgets, as well as biogeochemical fluxes of nitrogen and phosphorus were calculated using the LOICZ budget model for the three sections of the lagoon identified by morphological constrains and salinity patterns. Laguna Larga is a choked lagoon with restricted water circulation, low exchange, and high residence times that vary significantly along its sections. Residence time was estimated to be 0.1–0.7 years for the inner section and 1–9 days for the outer one. High levels of total nitrogen (annual means 126–137 μM, peaks up to 475 μM) and phosphorus (2.5–4.4 μM, peaks up to 14.5 μM) are evidence of eutrophication of Laguna Larga. During 2007, an average precipitation year, Laguna Larga exported water (703 m³ d^?1) and was a source of nitrogen (9.026 mmol m^?2 d^?1) and phosphorus (0.112 mmol m^?2 d^?1) to the adjacent sea. δ¹⁵N determinations in the seagrass Thalassia testudinum (?1.83 to +3.02?‰) differed significantly between sites in the lagoon and offshore reference sites located W of the inlet, but were similar to those located E of the inlet. δ¹⁵N determinations in the seaweed Penicillus dumetosus (+1.02 to +4.2) did not show significant differences.     

Evaluation of optimal conditions for determination of low selenium content in shellfish samples collected at Todos os Santos Bay,Bahia, Brazil using HG-AFS

This work proposes a procedure for the determination of total selenium content in shellfish after digestion of samples in block using cold finger system and detection using atomic fluorescent spectrometry coupled hydride generation (HG AFS). The optimal conditions for HG such as effect and volume of prereduction KBr 10 % (m/v) (1.0 and 2.0 ml) and concentration of hydrochloric acid (3.0 and 6.0 mol L^?1) were evaluated. The best results were obtained using 3 mL of HCl (6 mol L^?1) and 1 mL of KBr 10 % (m/v), followed by 30 min of prereduction for the volume of 1 mL of the digested sample. The precision and accuracy were assessed by the analysis of the Certified Reference Material NIST 1566b. Under the optimized conditions, the detection and quantification limits were 6.06 and 21.21 μg kg^?1, respectively. The developed method was applied to samples of shellfish (oysters, clams, and mussels) collected at Todos os Santos Bay, Bahia, Brazil. Selenium concentrations ranged from 0.23?±?0.02 to 3.70?±?0.27 mg kg^?1 for Mytella guyanensis and Anomalocardia brasiliana, respectively. The developed method proved to be accurate, precise, cheap, fast, and could be used for monitoring Se in shellfish samples.     

Flow injection online spectrophotometric determination of uranium after preconcentration on XAD-4 resin impregnated with nalidixic acid

In this work, spectrophotometer was used as a detector for the determination of uranium from water, biological, and ore samples with a flow injection system coupled with solid phase extraction. In order to promote the online preconcentration of uranium, a minicolumn packed with XAD-4 resin impregnated with nalidixic acid was utilized. The system operation was based on U(VI) ion retention at pH 6 in the minicolumn at flow rate of 15.2 mL min^?1. The uranium complex was removed from the resin by 0.1 mol dm^?3 HCl at flow rate of 3.2 mL min^?1 and was mixed with arsenazo III solution (0.05 % solution in 0.1 mol dm^?3 HCl, 3.2 mL min^?1) and driven to flow through cell of spectrophotometer where its absorbance was measured at 651 nm. The influence of chemical (pH and HCl (as eluent and reagent medium) concentration) and flow (sample and eluent flow rate and preconcentration time) parameters that could affect the performance of the system as well as the possible interferents was investigated. At the optimum conditions for 60 s preconcentration time (15.2 mL of sample volume), the method presented a detection limit of 1.1 μg L^?1, a relative standard deviation (RSD) of 0.8 % at 100 μg L^?1, enrichment factor of 30, and a sample throughput of 42 h^?1, whereas for 300 s of the preconcentration time (76 mL of sample volume), a detection limit of 0.22 μg L^?1, a RSD of 1.32 % at 10 μg L^?1, enrichment factor of 150, and a sampling frequency of 11 h^?1 were reported.     

UV/H2O2 oxidation of arsenic and terbuthylazine in drinking water

Arsenic is a widespread contaminant in the environment. The intake of water containing high concentrations of arsenic could have serious impact on human health, such as skin and lung cancer. In the European Union, thus, also in Italy, the arsenic limit in drinking water is 10 μg L^?1. Several water remediation treatment technologies are available for arsenic removal. For some processes, the removal efficiencies can be improved after an oxidation step. Most full-scale applications are based on conventional oxidation processes for chemical micropollutant removal. However, if water contains arsenic and refractory organic contaminants, the advanced oxidation processes could be considered. The aim of this work was to investigate the effectiveness of ultraviolet (UV) radiation alone and in combination with hydrogen peroxide for the oxidation of arsenic and terbuthylazine (TBA). The experimental tests were performed in groundwater at the laboratory scale (0.1 mg L^?1 As(III) and 10 μg L^?1 TBA). Hydrogen peroxide alone (15 mg L^?1) was ineffective on both arsenic and TBA oxidation; the 253.7-nm radiation alone did not oxidize arsenic(III), but photolyzed efficiently TBA (52 % removal yield at a UV dose of 1,200 mJ cm^?2). The UV/H₂O₂ advanced oxidation (UV dose 600–2,000 mJ cm^?2, 5–15 mg L^?1 H₂O₂) was the most effective process for the oxidation of both arsenic and TBA, with observed oxidation efficiencies of 85 and 94 %, respectively, with 5 mg L^?1 H₂O₂ and a UV dose of 2,000 mJ cm^?2.     

Seasonal perspective of dietary arsenic consumption and urine arsenic in an endemic population

Exposure to arsenic in arsenic endemic areas is most remarkable environmental health challenges. Although effects of arsenic contamination are well established, reports are unavailable on probable seasonal variation due to changes of food habit depending on winter and summer seasons, especially for endemic regions of Nadia district, West Bengal. Complete 24-h diets, drinking–cooking water, first morning voided urine samples, and diet history were analyzed on 25 volunteers in arsenic endemic Chakdah block of Nadia district, once in summer followed by once in winter from the same participants. Results depicted no seasonal variation of body weight and body mass index. Arsenic concentration of source drinking and cooking water decreased (p?=?0.04) from 26 μg L^?1 in summer to 6 μg L^?1 in winter season. We recorded a seasonal decrease of water intake in male (3.8 and 2.5 L day ^?1) and female (2.6 and 1.2 L day^?1) participants from summer to winter. Arsenic intake through drinking water decreased (p?=?0.04) in winter (29 μg day^?1) than in summer (100 μg day^?1), and urinary arsenic concentration decreased (p?=?0.018) in winter (41 μg L^?1) than in summer (69 μg L^?1). Dietary arsenic intake remained unchanged (p?=?0.24) over the seasons. Hence, we can infer that human health risk assessment from arsenic needs an insight over temporal scale.     

Hazard assessment of metals in invasive fish species of the Yamuna River,India in relation to bioaccumulation factor and exposure concentration for human health implications

Monitoring of heavy metals was conducted in the Yamuna River considering bioaccumulation factor, exposure concentration, and human health implications which showed contamination levels of copper (Cu), lead (Pb), nickel (Ni), and chromium (Cr) and their dispersion patterns along the river. Largest concentration of Pb in river water was 392 μg L^?1; Cu was 392 μg L^?1 at the extreme downstream, Allahabad and Ni was 146 μg L^?1 at midstream, Agra. Largest concentration of Cu was 617 μg kg^?1, Ni 1,621 μg kg^?1 at midstream while Pb was 1,214 μg kg^?1 at Allahabad in surface sediment. The bioconcentration of Cu, Pb, Ni, and Cr was observed where the largest accumulation of Pb was 2.29 μg kg^?1 in Oreochromis niloticus and 1.55 μg kg^?1 in Cyprinus carpio invaded at Allahabad while largest concentration of Ni was 174 μg kg^?1 in O. niloticus and 124 μg kg^?1 in C. carpio in the midstream of the river. The calculated values of hazard index (HI) for Pb was found more than one which indicated human health concern. Carcinogenic risk value for Ni was again high i.e., 17.02?×?10^?4 which was larger than all other metals studied. The results of this study indicated bioconcentration in fish due to their exposures to heavy metals from different routes which had human health risk implications. Thus, regular environmental monitoring of heavy metal contamination in fish is advocated for assessing food safety since health risk may be associated with the consumption of fish contaminated through exposure to a degraded environment.     

Preconcentration of metal ions through chelation on a synthesized resin containing O, O donor atoms for quantitative analysis of environmental and biological samples

Nascent Amberlite XAD-4 has been used as the polymeric support for the synthesis of a stable extractor of metal ions, by incorporating phthalic acid through azo bridging. Elemental analyses and infra-red spectral and thermal studies were carried out for its characterization. The water regain value and hydrogen ion capacity were found to be 12.50 and 5.75 mmol g^?1, respectively. The optimum pH range for the maximum sorption of Ni(II), Mn(II), Cu(II), Zn(II), Cd(II), Cr(III), and Co(II) was observed at pH 5.5–8.0 with the corresponding half-loading time (t _1/2) of 9, 5, 9, 9, 3, 9, and 5 min, respectively. The preconcentration factor for Ni(II), Mn(II), Cu(II), Zn(II), Cd(II), Cr(III), and Co(II) are 190, 190, 190, 180, 180, 160, and 160, with the corresponding limit of preconcentration in the range of 5.25–6.25 μg L^?1. The detection limits, for flame atomic absorption spectrophotometry, were found to be 0.62, 0.60, 0.65, 0.75, 0.72, 0.84, and 0.85 μg L^?1, respectively. Method has been successfully applied to the analysis of water samples, multivitamin formulations, infant food substitutes, hydrogenated oil, and fishes.     

Extraction of ultra traces of polychlorinated biphenyls in aqueous samples using suspended liquid-phase microextraction and gas chromatography-electron capture detection

This study reports the feasibility of applying directly suspended liquid-phase microextraction (DSLPME)-gas chromatography detection for the pre-concentration and determination of low levels of eight polychlorinated biphenyls (PCBs) in aqueous samples. The technique requires minimal sample preparation, analysis time and solvent consumption and represents significant advantages over conventional analytical methods. The experimental parameters such as salt content, sample temperature, stirring rate, extraction time, micro-drop volume and breakthrough volume were investigated and found to have significant influences on DSLPME. Under the optimal experimental conditions, the enrichment factor ranged from 578 to 729, and the recovery was above 93 %. Calibration curves possessed good linearity (R ²?>?0.99) over a wide concentration range of 0.1–10.0 μg L^?1 with limits of detection ranging from 0.01 to 0.07 μg L^?1. The relative standard deviations for 1.0 μg L^?1 of PCBs in water by using internal standard were in the range 2–14 % (n?=?3). The proposed simple, accurate and sensitive analytical method was applied successfully to the determination of trace amounts of PCBs in water samples.     

The evaluation of the association constant between R-SN and Hg2+

The effective determination of heavy metals from environmental media is among the most important issues for many industrialized countries. The interaction between RS-N, as novel heavy metal probe, and metal ions was studied. RS-N shows selective color change from colorless to pink in the presence of Hg²⁺ in methanol/water solvent and the UV–Vis study shows peak at 560 nm. Fluorescence data revealed that the fluorescence enhance of RS-N by Hg²⁺ dramatically was the result of the formation of [Hg²⁺]RS-N complex. The effective association constants (K _a ) were 3.97?×?10⁵ and 0.204?×?10⁵ M^?1 for Hg²⁺ and Cu²⁺ to RS-N, respectively. The thermodynamic parameters, enthalpy change (ΔH ⁰) and entropy change (ΔS ⁰), were calculated to be ?6.431?±?0.226 kJ/mol and ?0.129?±?0.008 J/K/mol, respectively, according to van’t Hoff equation on the basis of Gibbs free energy (ΔG ⁰) ranged from ?33.8326 to ?28.5389 kJ/mol.     

Stability of lysosomal membrane in Carcinus maenas acts as a biomarker of exposure to pharmaceuticals

The presence of pharmaceuticals in the environment is now a major concern given their potential adverse effects on organisms, particularly human beings. Because the feeding style and habitat of the crab Carcinus maenas make this species vulnerable to organic contaminants, it has been used previously in ecotoxicological studies. Lysosomal membrane stability (LMS) in crabs is a general indicator of cellular well-being and can be visualized by the neutral red retention (NRR) assay. LMS in crab hemolymph has been evaluated as a cellular biomarker of adverse effects produced by exposure to pharmaceutical compounds. Crabs were exposed in the laboratory to four different pharmaceuticals for 28 days in a semistatic 24-h renewal assay. Filtered seawater was spiked every 2 days with various concentrations (from 0.1 to 50 μg·L^?1) of caffeine, ibuprofen, carbamazepine, and novobiocin. Results showed that NRR time, measured at day 28, was significantly reduced (p?<?0.05) after exposure to environmental concentrations of each pharmaceutical (caffeine?=?15 μg·L^?1; carbamazepine?=?1 μg·L^?1; ibuprofen?=?5 μg·L^?1; and novobiocin?=?0.1 μg·L^?1) when compared with control organisms. The predicted “no environmental effect” concentration/measured environmental concentration results showed that the selected pharmaceuticals are toxic at environmental concentrations and need further assessment. LMS monitoring in crabs is a sensitive tool for evaluating exposure to concentrations of selected drugs under laboratory conditions and provides a robust tier 1 testing approach (screening biomarker) for rapid assessment of marine pollution and environmental impact assessments for analyzing pharmaceutical contamination in aquatic environments.     

Assessment of cylindrospermopsin toxin in an arid Saudi lake containing dense cyanobacterial bloom

This study reports the presence of the cyanobacterial toxin cylindrospermopisn (CYN) and its producer Cylindrospermopsis raciborskii for the first time in Saudi freshwater sources. C. raciborskii was found in Gazan Dam Lake water with two morphotypes (coiled and straight). The appearance and cell density of this species was significantly positively related to high temperature and high ammonium concentrations, and negatively with nitrate and phosphate concentrations in the lake. Intracellular concentrations of CYN (4–173 μg L^?1) were associated with C. raciborskii rather than other cyanobacteria with a maximal value obtained in June 2011, coinciding with the highest bloom of this species (19?×?10⁷ trichome L^?1). CYN cell quotas (0.6–14.6 pg cell^?1) varied significantly along the study period and correlated with most environmental factors. The results of ELISA and liquid chromatography-mass spectrometry proved that the CYN production by strains of this species was isolated from this lake during the present study, with an amount reaching 568 μg g^?1. Extracellular CYN was also detected in cell-free lake water at concentrations 0.03–23.3 μg L^?1, exceeding the drinking water guideline value of 1 μg L^?1 during the Apr–Jul period. As this lake is an important source for drinking and irrigation waters, CYN monitoring should be included in the environmental and health risk assessment plans of these water bodies.     

Solid-phase extraction and separation procedure for trace aluminum in water samples and its determination by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS)

In the present study, a separation/preconcentration procedure for determination of aluminum in water samples has been developed by using a new atomic absorption spectrometer concept with a high-intensity xenon short-arc lamp as continuum radiation source, a high-resolution double-echelle monochromator, and a charge-coupled device array detector. Sample solution pH, sample volume, flow rate of sample solution, volume, and concentration of eluent for solid-phase extraction of Al chelates with 4-[(dicyanomethyl)diazenyl] benzoic acid on polymeric resin (Duolite XAD-761) have been investigated. The adsorbed aluminum on resin was eluted with 5 mL of 2 mol L^-1 HNO₃ and its concentration was determined by high-resolution continuum source flame atomic absorption spectrometry (HR-CS FAAS). Under the optimal conditions, limit of detection obtained with HR-CS FAAS and Line Source FAAS (LS-FAAS) were 0.49 μg L^?1 and 3.91 μg L^?1, respectively. The accuracy of the procedure was confirmed by analyzing certified materials (NIST SRM 1643e, Trace elements in water) and spiked real samples. The developed procedure was successfully applied to water samples.     

Aircraft mass budgeting to measure CO2 emissions of Rome,Italy

Aircraft measurements were used to estimate the CO₂ emission rates of the city of Rome, assessed against high-resolution inventorial data. Three experimental flights were made, composed of vertical soundings to measure Planetary Boundary Layer (PBL) properties, and circular horizontal transects at various altitudes around the city area. City level emissions and associated uncertainties were computed by means of mass budgeting techniques, obtaining a positive net CO₂ flux of 14.7?±?4.5, 2.5?±?1.2, and 10.3?±?1.2 μmol m^?2 s^?1 for the three flights. Inventorial CO₂ fluxes at the time of flights were computed by means of spatial and temporal disaggregation of the gross emission inventory, at 10.9?±?2.5, 9.6?±?1.3, and 17.4?±?9.6 μmol m^?2 s^?1. The largest differences between the two dataset are associated with a greater variability of wind speed and direction in the boundary layer during measurements. Uncertainty partitioned into components related to horizontal boundary flows and top surface flow, revealed that the latter dominates total uncertainty in the presence of a wide variability of CO₂ concentration in the free troposphere (up to 7 ppm), while it is a minor term with uniform tropospheric concentrations in the study area (within 2 ppm). Overall, we demonstrate how small aircraft may provide city level emission measurements that may integrate and validate emission inventories. Optimal atmospheric conditions and measurement strategies for the deployment of aircraft experimental flights are finally discussed.     

Coupling of solvent-based de-emulsification dispersive liquid–liquid microextraction with high performance liquid chromatography for simultaneous simple and rapid trace monitoring of 2,4-dichlorophenoxyacetic acid and 2-methyl-4-chlorophenoxyacetic acid

A simple, rapid, and efficient sample pretreatment technique, based on solvent-based de-emulsification dispersive liquid–liquid microextraction (SD-DLLME), followed by high performance liquid chromatography (HPLC) has been developed for simultaneous preconcentration and trace detection of 2,4-dichlorophenoxyacetic acid (2,4-D) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in water and urine samples. Some parameters such as acidity of solution, the amount of salt, type, and volume of extraction solvents, type of disperser/de-emulsifier solvent, and its volume were investigated and optimized. Under optimum extraction conditions, the limits of detections (LODs) of this method for MCPA and 2,4-D were 0.2 and 0.6 μg L^?1 (based on 3S_b/m) in water and 0.4 and 1.6 μg L^?1 in urine, respectively. Furthermore, dynamic linear range of this method for MCPA and 2,4-D was 1–300 and 2–400 μg L^?1, repectively. Finally, the applicability of the proposed method was evaluated by extraction and determination of the herbicides in urine and different water samples.