Rapid spectrophotometric determination of trace amounts of palladium in water samples after dispersive liquid–liquid microextraction

A simple, rapid, and efficient dispersive liquid–liquid microextraction method, followed by UV–Vis spectrophotometry was developed for the preconcentration and determination of Pd ions in water samples. Pd ions react with α-furildioxime (chelating agent) to form a hydrophobic complex. Various parameters were altered to study and optimize their effects on the extraction efficiency, such as pH, ligand concentration, the type and volume of extraction and dispersive solvents, extraction time, and salt concentration. Under optimized conditions, the method exhibited an enrichment factor (C _org/C _aq) of 25 and recovery more than 98 % within a very short extraction time. The linearity of the method ranged from 10 to 200 μg?L^?1. The limit of detection was 1.1 μg?L^?1. The relative standard deviation for the concentration of 100 μg?L^?1 of Pd was 2.3 % (n?=?10). Finally, the developed method was successfully applied to the extraction and determination of Pd in tap, river, mineral, and sea water samples.     

Monitoring of copper level in water and soil samples by using liquid–liquid extraction

A new, simple, sensitive, and selective spectrophotometric method for the determination of copper in water and soil samples has been demonstrated. The method is based on the reaction of Cu(I) with neocuproine (2,9-dimethyl-1, 10-phenanothroline) and extracted with N-phenyl benzimidoylthiourea in chloroform. The value of molar absorptivity of the complex in the term of Cu(I) is 1.45 × 10⁵ L mol^???1 cm^???1 at λ _max 460 nm in chloroform. The detection limit of copper in water and soil is 2 ng mL^???1 and 4 ng g^???1, respectively. The method is free from the interference of the ions commonly found to be associated with the copper determination in water and soil samples. The application of the proposed method has been successfully tested for the determination of copper in different types of water and soil samples.     

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.     

Assessment of liquid disposal originated by uranium enrichment at Aramar Experimental Center São Paulo--Brazil

This work presents a liquid disposal monitoring originated from uranium enrichment process at Aramar Experimental Center from 1990 to 1998. Assessment of uranium, fluorides, ammoniacal nitrogen, chemical oxygen demand, and pH measurements were made in water samples and compared with results achieved in other countries, as North America and India. The liquid disposal evaluation, generated by uranium enrichment process, showed low levels, considering most parameters established by Federal and State Legislation, aiming environmental pollution control. However, uranium levels were above the limits established by Conselho Nacional do Meio Ambiente, Environment Protection Agency and mainly by the World Health Organization.     

Estimation of chlorpyriphos and cypermethrin residues in chilli (Capsicum annuum L.) by gas–liquid chromatography

Dissipation of chlorpyriphos and cypermethrin in chilli was studied following three applications of a combination formulation of Nurelle-D 505 (chlorpyriphos 50 %?+?cypermethrin 5 %) at 1 and 2 L?ha^?1 at an interval of 15 days. Residues of chlorpyriphos and cypermethrin in chilli were estimated by gas–liquid chromatography and confirmed by gas chromatography–mass spectrometry. Half-life periods for chlorpyriphos were found to be 4.43 and 2.01 days, whereas for cypermethrin these values were observed to be 2.51 and 2.64 days at single and double the application rates, respectively. Residues of chlorpyriphos dissipated to more than 80 % after 10 days at both the dosages. However, residues of cypermethrin dissipated to the extent of more than 70 % in 7 days. Soil samples collected after 15 days of the last application did not show the presence of chlorpyriphos and cypermethrin at their respective determination limit of 0.01 mg?kg^?1. The use of chlorpyriphos and cypermethrin mixture at the recommended dosage does not seem to pose any hazards to the consumers, and a waiting period of 1 day is suggested to reduce the risk before consumption of green chilli.     

Optimization and determination of Cd (II) in different environmental water samples with dispersive liquid�Cliquid microextraction preconcentration combined with inductively coupled plasma optical emission spectrometry

Dispersive liquid?Cliquid microextraction followed by inductively coupled plasma-optical emission spectrometry has been investigated for determination of Cd(II) ions in water samples. Ammonium pyrrolidine dithiocarbamate was used as chelating agent. Several factors influencing the microextraction efficiency of Cd (II) ions such as extracting and dispersing solvent type and their volumes, pH, sample volume, and salting effect were optimized. The optimization was performed both via one variable at a time, and central composite design methods and the optimum conditions were selected. Both optimization methods showed nearly the same results: sample size 5 mL; dispersive solvent ethanol; dispersive solvent volume 2 mL; extracting solvent chloroform; extracting solvent volume 200  $\upmu $ L; pH and salt amount do not affect significantly the microextraction efficiency. The limits of detection and quantification were 0.8 and 2.5 ng L^???1, respectively. The relative standard deviation for five replicate measurements of 0.50 mg L^???1 of Cd (II) was 4.4%. The recoveries for the spiked real samples from tap, mineral, river, dam, and sea waters samples ranged from 92.2% to 104.5%.     

Community air monitoring for pesticides—part 2: multiresidue determination of pesticides in air by gas chromatography,gas chromatography–mass spectrometry,and liquid chromatography–mass spectrometry

Two multiresidue methods were developed to determine pesticides in air collected in California. Pesticides were trapped using XAD-4 resin and extracted with ethyl acetate. Based on an analytical method from the University of California Davis Trace Analytical Laboratory, pesticides were detected by analyzing the extract by gas chromatography–mass spectrometry (GC-MS) to determine chlorothalonil, chlorthal-dimethyl, cycloate, dicloran, dicofol, EPTC, ethalfluralin, iprodione, mefenoxam, metolachlor, PCNB, permethrin, pronamide, simazine, trifluralin, and vinclozolin. A GC with a flame photometric detector was used to determine chlorpyrifos, chlorpyrifos oxon, diazinon, diazinon oxon, dimethoate, dimethoate oxon, fonophos, fonophos oxon, malathion, malathion oxon, naled, and oxydemeton. Trapping efficiencies ranged from 78 to 92 % for low level (0.5 μg) and 37–104 % for high level (50 and 100 μg) recoveries. Little to no degradation of compounds occurred over 31 days; recoveries ranged from 78 to 113 %. In the California Department of Food and Agriculture (CDFA) method, pesticides were detected by analyzing the extract by GC-MS to determine chlorothalonil, chlorpyrifos, cypermethrin, dichlorvos, dicofol, endosulfan 1, endosulfan sulfate, oxyfluorfen, permethrin, propargite, and trifluralin. A liquid chromatograph coupled to a MS was used to determine azinphos-methyl, chloropyrifos oxon, DEF, diazinon, diazinon oxon, dimethoate, dimethoate oxon, diuron, EPTC, malathion, malathion oxon, metolachlor, molinate, norflurazon, oryzalin, phosmet, propanil, simazine and thiobencarb. Trapping efficiencies for compounds determined by the CDFA method ranged from 10 to 113, 22 to 114, and 56 to 132 % for 10, 5, and 2 μg spikes, respectively. Storage tests yielded 70–170 % recovery for up to 28 days. These multiresidue methods represent flexible, sensitive, accurate, and cost-effective ways to determine residues of various pesticides in ambient air.     

Evaluation of Mass-Transfer Coefficient of Free Fall – Cascade-Aerator

The mass-transfer coefficient of a free-fall cascade-aeratorunit of 15 million litres per day was evaluated for its efficiency in the removal of a class of volatile organics, the trihalomethanes(THMs). These compounds are carcinogenic and occur as a resultof chlorination of natural waters. Due to the volatile nature ofthe THMs, the efficiency of aeration as a potential techniquefor their removal has been studied. The principle behindaeration is gas-transfer, according to which the gas-liquidinterface is hypothesized to consist of a gas and liquid filmthrough which gas is transferred by molecular diffusion untilequilibrium is attained. The overall mass transfer coefficient(K _L) of the aerator considering oxygen as the reference compound, was found to be29.3 hr^-1 for THMs.     

Simulation of impact of oil spill in the ocean – a case study of Arabian Gulf

To meet the growing energy demand worldwide, oil and gas exploration and production activities have increased rapidly both in onshore and offshore areas. The produced oil from the ocean bed is transported onshore either by ship or pipeline. This has increased the risk of oil spill in the coastal area. In order to prepare an emergency preparedness plan and to assess the magnitude of risk involved in transporting and offloading oil, oil spill simulation studies play an important role. This paper describes a simulation of oil spill in coastal bay of Arabian Gulf where new developments are taking place using MIKE 21 model. The developments include a diesel based thermal power plant near Sir Baniyas Island, which is an ecological fragile area. Based on the project activity, two probable scenarios, one for diesel leak (250 m3/h) for 1 h and the other for instantaneous spill (500 m3) are considered. The MIKE 21 model was calibrated for hydrodynamics using measured field data followed by diesel-spill simulation to track its movement in the Arabian Gulf. The results for both leak and instantaneous spill indicate that spilled diesel will not move towards the Sir Banyas Island and more than 45% of the diesel will be evaporated within 48 h of oil spill. Based on the results, a clean up and contingency plan is proposed to mitigate the adverse impacts arising due to diesel spill in the study area.     

Analysis of heavy metal concentrations in sediments of selected estuaries of Malaysia—a statistical assessment

Statistical analysis of heavy metal concentrations in sediment was studied to understand the interrelationship between different parameters and also to identify probable source component in order to explain the pollution status of selected estuaries. Concentrations of heavy metals (Cu, Zn, Cd, Fe, Pb, Cr, Hg and Mn) were analyzed in sediments from Juru and Jejawi Estuaries in Malaysia with ten sampling points of each estuary. The results of multivariate statistical techniques showed that the two regions have different characteristics in terms of heavy metals selected and indicates that each region receives pollution from different sources. The results also showed that Fe, Mn, Cd, Hg, and Cu are responsible for large spatial variations explaining 51.15% of the total variance, whilst Zn and Pb explain only 18.93 of the total variance. This study illustrates the usefulness of multivariate statistical techniques for evaluation and interpretation of large complex data sets to get better information about the heavy metal concentrations and design of monitoring network.     

Evaluation of environmental impacts of Integrated Industrial Estate��Pantnagar through application of air and water quality indices

Large-scale industrialization, population inflow, and rapid urbanization coupled with unfavorable meteorological conditions often induce significant degradation of urban environment. In order to assess the extent of environmental impacts due to establishment of the Integrated Industrial Estate??Pantnagar (IIE-Pantnagar), ambient air and groundwater were monitored from June 2007 to May 2008. Collected baseline information was normalized and interpreted with the application of air (AQI) and water quality indices (WQI). Among the pre-identified air pollutants, suspended particulate matter was found to be the principal culprit to deteriorate ambient air quality, with a maximum annual concentration of 418.5 ??g/m³. Monthly average concentrations of respirable particulate matter (aerodynamic diameter < 10 ??m) also persist at a critical level with an annual maximum of 207.3 ??g/m³. A segmented linear function with maximum operator concept was used to compute AQI, and the developed index was found well suitable to demonstrate temporal variations of ambient air quality. The computed AQI value for the selected study region varied from moderate (97.0) to very poor pollution level (309.2) in respect to developed air quality standards. Furthermore, an integrated WQI was developed comprising 9 parameters, and among all the 10 pre-identified locations, the average groundwater quality was found acceptable in terms of Indian drinking water standards. The maximum WQI (70.6) was found at the Kichha Railway Station during summer months, revealing moderate pollution load. Industrial discharge from IIE-Pantnagar coupled with other industrial setup may hold responsible for such kind of degradation of water quality. In contrast, WQI computed at Rudrapur City demonstrate minimum (15.0?C22.1) pollution load. For 95% of the monitoring period, the computed WQI was found acceptable for all selected locations with few exceptions. The application of WQI to assess temporal variations in groundwater quality was therefore found satisfactory.     

Time trend of Butyl- and Phenyl-Tin contamination in organisms of the Lagoon of Venice (1999–2003)

In the period 1999-2003 a monitoring study on the accumulation of organotin compounds in edible organisms in the Lagoon of Venice was conducted. Butyl and Phenyl derivatives were determined in pooled samples of Mytilus galloprovincialis and Tapes spp. with the aims of assessing organotin contamination in the Lagoon of Venice in the period just preceding their ban in Europe, monitoring the concentrations in organisms with a high commercial use, evaluating a potential hazard for human health due to seafood and identifying the possible contamination sources. Sampling stations (up to 20) were distributed around the Lagoon and particularly concentrated in the area close to the town of Chioggia. Significantly higher (analysis of variance (ANOVA), p < 0.05) tributyltin (TBT) concentrations were found in mussels (from 38 +/- 8 to 6,666 +/- 1,333 microg kg(-1) d.w., as TBT(+)), than in clams (from 6 +/- 1 to 2,256 +/- 451 microg kg(-1) d.w., as TBT(+)). During the 3 years of the survey no increase in average concentrations of the butyltin compounds (tributyltin (TBT) + dibutyltin (DBT) + monobutyltin (MBT)) was observed (ANOVA, p > 0.05) in either species. Furthermore, by analyzing the entire data set, it is evident that most stations show analogous concentrations in the 3 years for both species, whereas few have anomalously higher concentrations. If organotin concentrations in specimens from some sites are compared with the Tolerable Average Residue Level, a possible risk for human health must be considered.     

“Emission game”: some applications of the theory of games to the problem of CO2 emission

If there are no doubts that we must reduce the total emission of carbon dioxide, then the problem of how much different countries should be allowed to contribute to this amount remains a serious one. We suggest this problem to be considered as a non-antagonistic game (in Germeier's sense). A game of this kind is called an “emission game”. Suppose that there are n independent actors (countries or regions), each of them releasing a certain amount of CO₂ per year (in carbon units) into the atmosphere, and that the emission would be reduced by each actor. Each actor has his own aim: to minimise the loss in the Gross Domestic Product (GDP) caused by the reduction of emissions. On the other hand, taking into account that it is impossible to estimate more or less precisely the impact of the climate change on GDP for each country today, a common strategy will be to reduce the climate change. Since one of the main leading factors in global warming is the greenhouse effect, then the common aim will be to reduce the sum of emissions. This is a typical conflict situation. How to resolve it? We can weigh the “egoistic” and “altruistic” criteria for each actor introducing the so-called “coefficients of egoism”. This coefficient is very large, if the actor uses a very egoistic strategy, and conversely, if the actor is a “super-altruist”, then the corresponding coefficient is very small. Using these coefficients we get the general solution of the game in a form of some Pareto's equilibrium. The solution is stable and efficient.     

Analysis of acidic components, heavy metals and PAHS of particulate in the Changwon–Masan area of Korea

This study is an analysis of the concentrations and components of heavy metals in PM_2.5 and the total suspended particulate (TSP) collected at a mechanical industrial complex (IC) site in Changwon and at a residential site in Masan, Korea. Particulate was collected during two sampling periods, from the late summer to the early fall and from the middle to late fall, at the IC site and one sampling period, from the middle fall to the early winter, at the residential site. PM_2.5 and TSP samples were taken by an annular denuder system and a hi-volume air sampler, respectively. The authors also identified the concentrations and components of heavy metals extracted from the PM_2.5 and TSP filters, the acidic components extracted from the PM_2.5 filters, and the polycyclic aromatic hydrocarbons (PAHs) extracted from polyurethane foam (PUF) plug. The average concentrations of the PM_2.5 collected at the IC and residential sites were very similar. Major sources of PM_2.5 at the study sites, however, were air emissions from vehicles and industry as well as emissions from residential heating and soil origins, respectively. The higher concentrations of the TSP at the IC site, as compared to those at the residential site, were due to either increased suspended dust from vehicle emissions or re-suspended road dust because of increased vehicle speeds near the IC site. Heavy metal concentrations in the TSPs were higher than those in the PM_2.5. The heavy metal concentrations in the PM_2.5 and TSP at the IC site with heavy traffic were substantially greater than those at the residential site. The concentrations of TSP and heavy metals and PAHs in PM during the period of the middle to late fall was much higher than those during the period of the late summer to early fall at the IC site. This is because of the difference in meteorological characteristics and energy uses between two periods. The residential site also showed higher concentrations of acidic anions while the IC site showed higher concentrations of acidic cation. Secondary aerosols or particulates, such as ammonium nitrate or ammonium nitrite, might have been important constituents of the PM_2.5 at the residential site. The PAHs in the TSP collected at the IC site was greatly affected by traffic and industry emissions consisting mostly of high molecular weight PAHs with two to four rings. PAHs in the TSP at the site, however, were affected by residential heating and air emissions from small chemical plants having higher concentrations of low molecular weight PAHs with five to six rings.     

Comparison of Noniterative Algorithms Based on Different Forms of Richards’ Equation

Through linearizing an implicit differencing scheme, several noniterative numerical solutions of Richards’ equation in different forms are derived here. Paniconi et al. (Water Resources Research, 27(6), 1147–1163, 1991) have developed a first-order accurate linearization of the head-based Richards’ equation (RE) and a second-order accurate linearization of the implicit-factored head-based RE. Considering other forms of RE, we propose a second-order accurate linearization of the moisture-based RE and a second-order accurate linearization of the mixed form RE combined with the primary variable switching technique. Extensive comparisons between the noniterative solutions are conducted through three numerical experiments. Their accuracies, efficiencies, and mass balance behaviors are analyzed. The results indicate that the first-order accurate scheme is not efficient compared to iterative models. The noniterative schemes of head-based RE suffer from the mass imbalance problem without iteration. The linearized moisture-based RE can obtain mass conservative, accurate results effectively, while it may confront numerical problems when the soil approaches saturation. Among these noniterative schemes, the linearized mixed form RE combined with the primary variable switching technique is superior in terms of accuracy, mass balance, and efficiency compared to traditional iterative methods.     

Development of the concept of spatial–temporal mask for testing effects of discharge from well-drilling activities on biological communities

This paper describes the use of Bayesian spatial models to develop the concept of a spatial–temporal mask for the purpose of identifying regions in which before and after drilling effects are most clearly defined and from which the consequences of exposure of macrofauna and meiofauna to the release of drilling discharges can be evaluated over time. To determine the effects of drilling fluids and drill-cuttings on the marine benthic community, it is essential to know not only where discharged materials ended up within the possible impact area, but also the chemical concentrations to which biota were exposed during and after drilling. Barium and light hydrocarbons were used as chemical tracers for water-based and non-aqueous-based fluids in a shallow water site in the Campos Basin, off the coast of Brazil. Since the site showed evidence of exposure to waste material from earlier drilling, the analysis needed to take into account the background concentrations of these compounds. Using the Bayesian models, concentrations at unsampled sites were predicted and regions altered and previously contaminated were identified.     

Assessment of dietary intakes of nineteen pesticide residues among five socioeconomic sections of Hyderabad—a total diet study approach

Total diet study approach was used to assess the dietary intakes of pesticide residues among the select population in Hyderabad. When assessed by a food frequency questionnaire, it was found that the food intakes varied among five socioeconomic sections (SES). Therefore, we intended to compare the intakes of pesticide residues through these foods among the five SES. A total of 195 foods from different markets were collected and analyzed for 19 pesticides. The residues were analyzed with a gas chromatograph and were confirmed with mass spectrometry. About 51 % of the samples were detected with one or more residues. Thirteen out of the 19 residues were present in levels above detection limits in various concentrations. The median concentrations of the residues in all the samples tested, ranged from 0.00010 to 0.33 mg/kg. Highest median concentration was for β-HCH in water samples. Exposures to all the residues were below the respective ADIs at both mean and 95th percentile levels of food intakes with highest estimated dietary intakes (EDIs) of β-HCH in both the cases. The EDIs of β-HCH were the highest among all the residues at both the intake levels among all the SES. The EDIs of β-HCH were significantly higher in lower SES than higher SES possibly due to the consumption of rice cooked in water contaminated with β-HCH. EDIs for other residues did not differ significantly among the five SES.     

Speciation of Trace Metals in Coastal Sediments of El-Mex Bay South Mediterranean Sea–West of Alexandria (Egypt)

Sediments of El-Mex Bay estuary on the southern Mediterranean Sea have been analyzed for trace metals after sediment fractionation by sequential leaching. A sequential extraction procedure was applied to identify forms of Mn, Cu, Cd, Cr, Zn and Fe. The five steps of the sequential extraction procedure partitioned metals into: CH₃COONH₄ extractable (F1); NaOAC carbonate extractable (F2); NH₂OH.HCl/CH₃COOH reducible extractable (F3); H₂O₂–HNO₃ organic extractable (F4) and NHO₃/HClO₄/HF acid soluble residue (F5). Extracted concentrations of trace metals analyzed after all five steps, were found to be (μg/g) for Mn: 1930.2, Cu: 165.3, Cd: 60.9, Cr: 386.3, Zn: 2351.3 and Fe: 10895. Most of elements were found in reducible fraction except Fe found in acid soluble residue, characterizing stable compounds in sediments. Labile (non-residual) fractions of trace elements (sum of the first four fractions) were analyzed because they are more bioavailable than the residual amount. Correlation analysis was used to understand and visualize the associations between the labile fractions of trace metals and certain forms, since Fe-and Mn-oxides play an important role in trace metals sorption within aquatic systems, especially within El-Mex Bay sediments that characterized by varying metal bioavailability.     

Extraction of soil solution by drainage centrifugation—effects of centrifugal force and time of centrifugation on soil moisture recovery and solute concentration in soil moisture of loess subsoils

The solute concentration in the subsoil beneath the root zone is an important parameter for leaching assessment. Drainage centrifugation is considered a simple and straightforward method of determining soil solution chemistry. Although several studies have been carried out to determine whether this method is robust, hardly any results are available for loess subsoils. To study the effect of centrifugation conditions on soil moisture recovery and solute concentration, we sampled the subsoil (1.5–3.0 m depth) at commercial farms in the loess region of the Netherlands. The effect of time (20, 35, 60, 120 and 240 min) on recovery was studied at two levels of the relative centrifugal force (733 and 6597g). The effect of force on recovery was studied by centrifugation for 35 min at 117, 264, 733, 2932, 6597 and 14,191g. All soil moisture samples were chemically analysed. This study shows that drainage centrifugation offers a robust, reproducible and standardised way for determining solute concentrations in mobile soil moisture in silt loam subsoils. The centrifugal force, rather than centrifugation time, has a major effect on recovery. The maximum recovery for silt loams at field capacity is about 40%. Concentrations of most solutes are fairly constant with an increasing recovery, as most solutes, including nitrate, did not show a change in concentration with an increasing recovery.