Quantitative structure–activity relationship methods for the prediction of the toxicity of pollutants

Environmental Chemistry Letters - Continuous flow of toxic and persistent compounds to the environment is a global health issue. However, assessing the toxic effects of compounds...     

Determination of pentachlorophenol in human urine using solid phase extraction and GC‐MS analysis with stable isotope dilution

A method for the determination of pentachlorophenol (PCP) in human urine was developed. Urine samples were fortified with ¹³C₆‐IabeIed PCP and hydrolyzed with sulfuric acid prior to extraction. The urine samples were then passed through preconditioned solid phase extraction cartridges containing octadecylsilane adsorbent. The PCP was subsequently eluted from the cartridge with ethyl acetate and converted to pentachloroanisole prior to GC‐MS analysis. GC‐MS quantitation was performed using the technique of stable isotope dilution. Percent recoveries averaging 100, 97, and 111% were obtained for replicate urine samples fortified with approximately 2, 20, and 200 ng/mL of PCP, respectively. The method detection limit was estimated to be 0.2 ng/mL.     

Detection of organic contamination in sediments by double-shoot pyrolysis–GC/MS

Pyrolysis coupled with gas chromatography–mass spectrometry (Py–GC–MS) has been previously proved to be an appropriate tool for the screening of organic contaminants in sediments. In this work the double-shoot pyrolysis technique has been applied to assess the contamination degree of sediment samples from Castro Marim Natural Park (South Portugal) and the Ria of Huelva (SW Spain). Compounds released both by thermodesorption at sub-pyrolysis temperatures (250–280°C) and subsequent pyrolysis (300–500°C) revealed information on the origin of the sedimentary organic matter and the occurrence of organic contamination in the sediments. Thermal desorption was found to be effective in releasing organic contaminants from spiked samples. However, in real sediments samples, higher pyrolysis temperatures (>300°C) were necessary to detect the occurrence of organic contaminants. Particularly polycyclic aromatic hydrocarbons (PAHs) and linear alkylbenzenes (LABs) were detected in variable proportions in most sediment samples.     

Planning for the monitoring of pollutants from non‐stationary combustion sources†

The most important constituents of traffic exhaust are carbon monoxide, nitrogen oxides, volatile organic compounds, polycyclic hydrocarbons and lead. Satisfactory analytical methods are available for measuring these compounds, but the required expenditure in their application to air pollution studies is quite different. Due to correlations between the concentrations of several exhaust components in road air conclusions regarding the expected level of some substances can be drawn by measurement of another emitted compound. But the selection of indicator compounds must be made under the aspect of the source‐specific relationship of emitted substances. The temporal and spatial distribution of air pollutants in street air is affected by traffic emissions more than by meteorological conditions. “Fingerprints”; of typical organic gaseous components of traffic exhaust also were found in residential areas.     

Halogenated organic compounds (volatile and non volatile) as parameters for the evaluation of drinking water quality)†

Trihalomethanes are a well known parameter of water quality, but the determinations of the other volatile organochlorine compounds and of total organic halogen can give us more complete informations. Results are given about their use for ground waters and for treated surface waters. Ground waters may be polluted by halogenated solvents. The choice of an oxidizing agent has a great influence upon the quality of treated river water.     

Analyses of phenolic compounds occurring in olive oil mill wastewaters by GC–MS

Phenolic compounds in olive oil mill wastewaters were analysed by HRGC–MS after extracting the acidified solution with ethyl acetate and derivatization with N,O-bis(trimethylsilyl)trifluoroacetamide. Both simple and complex phenols were detected with the latter being the most abundant. 1,2-dihydroxybenzene (catechol), p-hydroxyphenyl ethanol (tyrosol), 3,4-dihydroxyphenyl ethanol (hydroxytyrosol) and 4-hydroxy-3-methoxyphenyl ethanol (homovanillyl alcohol) predominated among the simple phenols using a gas chromatograph coupled with a mass selective detector.     

A Poisson–Gamma model for analysis of ecological non-negative continuous data

The statistical analysis of continuous data that is non-negative is a common task in quantitative ecology. An example, and our motivation, is the weight of a given fish species in a fish trawl. The analysis task is complicated by the occurrence of exactly zero observations. It makes many statistical methods for continuous data inappropriate. In this paper we propose a model that extends a Tweedie generalised linear model. The proposed model exploits the fact that a Tweedie distribution is equivalent to the distribution obtained by summing a Poisson number of gamma random variables. In the proposed model, both the number of gamma variates, and their average size, are modelled separately. The model has a composite link and has a flexible mean-variance relationship that can vary with covariates. We illustrate the model, and compare it to other models, using data from a fish trawl survey in south-east Australia.     

Endeavors on the development of efficient and sustainable supported metal catalysts for chemical synthesis on solid–liquid interfaces

Supported metal catalysts, particularly for precious metals, have gained increasing attention in green synthetic chemistry. They can make metal-catalyzed organic synthesis more sustainable and economical due to easy separation of product with less metal residue, as well as reusability of the high-cost catalysts. Although great effort has been spent, the precise catalytic mechanism of supported metal-catalyzed reactions has not been clearly elucidated and the development of efficient and stable r...     

A two-step local smoothing approach for exploring spatio-temporal patterns with application to the analysis of precipitation in the mainland of China during 1986–2005

There has been a growing interest on using local modelling techniques for the analysis of spatio-temporal data because of their powerfulness in extracting the underlying local patterns in the data. In this study, we propose a two-step local smoothing approach to explore spatial patterns and temporal trends of spatio-temporal data via combining the geographically weighted regression and the local polynomial smoothing procedure. The proposed method incorporates both spatial and temporal information into the calibration process and makes it easier to implement visualization of the results. A simulation experiment is conducted to assess the performance of the proposed method and the results show that the method works satisfactorily. A real-world spatio-temporal data set is analyzed to demonstrate the practical usefulness of the method.     

A sensitive method for selective determination of vanadium species by dispersive liquid–liquid microextraction (DLLME) with spectrophotometric detection

A simple, fast, and low-cost analytical procedure was developed for trace-level determination of inorganic vanadium species by dispersive liquid–liquid microextraction in combination with spectrophotometry. Vanadium in pentavalent form, V(V), was quantitatively extracted into organic phase as 4-(2-pyridylazo)-recorcinol (PAR) complex in the presence of N-cetyl-N,N,N-trimethyl ammonium bromide (CTAB) as counter-ion. Vanadium (IV) was masked with 1,2-diaminocyclohexanetetraacetic acid to allow speciation analysis. Total vanadium was determined after oxidation of V(IV) to V(V). The main factors affecting preconcentration and spectrophotometric detection of vanadium species such as pH, concentration of PAR and CTAB, the type and volume of the extraction, and disperser solvents were optimized. The limit of detection and enhancement factor obtained under optimum conditions were found to be 0.06 μg L^?1 and 98, respectively. Relative standard deviations for V(IV) and V(V) at 3.0 μg L^?1 were less than 2.4%. The presented procedure was applied to environmental water samples for selective determination of vanadium species. Moreover, the method was applied to determination of vanadium in edible salt samples, due to its applicability in high-NaCl-containing solutions. The validity of proposed method was proven by spike recovery experiments and also independent analysis by inductively coupled plasma mass spectrometry.     

Dispersive liquid–liquid microextraction of cadmium(II) for preconcentration prior to flame atomic absorption spectrometric detection in water

A dispersive liquid–liquid microextraction procedure for cadmium(II) as its 2-(5-bromo-2-pyridylazo)-5-diethylamino-phenol chelate is presented. Carbon tetrachloride and methanol were used as extraction and dispersive solvents, respectively. After phase separation, the preconcentrated-separated cadmium(II) is determined by flame atomic absorption spectrometry with a microinjection technique. The factors which affected the extraction efficiency, i.e. the pH of the sample solution and the volumes of reagent and sample were investigated. The effects of some alkali, alkali earth, and transition metal ions, and of some anions on the recovery of cadmium were also studied. A preconcentration factor of 250 was obtained for a sample volume of 50?mL under optimum conditions. The method was validated by analysis of certified reference materials and applied to some water samples from Turkey.     

Gas–liquid chromatography for fenvalerate residue analysis: alterations in the ionic concentration and associated adinosine triphosphatases in fish,Cirrhinus mrigala (hamilton)

In the present study, an attempt has been made to quantify the fenvalerate accumulated in different tissues (gill, muscle and liver) and observe changes involved in the levels of sodium, potassium and calcium ions and Na⁺–K⁺, Mg²⁺ and Ca²⁺ adenosine triphosphatase (ATPase) activities in the freshwater fish, Cirrhinus mrigala on short-term and long-term exposure to the median lethal and sublethal concentration of fenvalerate. Residue analysis using gas–liquid chromatography (GLC) technique revealed that fenvalerate accumulated in highest quantity in gill followed by liver and muscle under median lethal concentration (6?µg?L^?1). Whereas in sublethal concentration (0.6?µg?L^?1), muscle accumulated highest quantity followed by gill and liver, which might be due to the fact that fenvalerate is highly lyphophilic. The ion concentration and ATPase activity were found effected in fish exposed to lethal and sublethal concentrations of fenvalerate. Concentration of Na⁺, K⁺ and Ca²⁺ ions decreased in gill, muscle and liver on being exposed to median lethal concentration to a significant level. Whereas the changes were not highly pronounced at sub lethal level indicating low concentration of fenvalerate and its non-toxic effect at chronic exposure. Na⁺–K⁺, Mg²⁺ and Ca²⁺ ATPases activity were also found decreased in correspondence to the ionic change under median lethal and sub lethal concentrations in target tissues. This might have lead to behavioural changes and create wide-spread disturbance in the normal physiology, ultimately causing the death of the fish. The results suggest that in biomonitoring programmes, ions and associated ATPases can be a good diagnostic tool for fenvalerate toxicity.     

Quantitative gap analysis for the West Coast of Florida based on experts’ opinion

The primary objective of this study was to identify gaps in coastal and marine data available through the Gulf Geospatial Assessment of Marine Ecosystems (GAME) project for the west coast of Florida. A survey was designed and sent to more than 2,000 experts working with coastal and ocean issues in the Gulf of Mexico to elicit their opinions. The survey asked the experts to rank 12 data categories and score the relevance of four qualifiers (spatial resolution, temporal resolution, age of data, and level of detail) using a discrete choice approach. The statistical interpretation of experts?? responses allowed assigning a relative value to each available data set, based upon their qualifiers. The results were then displayed in a Geographic Information System to visually show how the total value for all data categories or for a specific data category varies spatially and to identify data gaps. It was found that the total data set value is generally higher within Tampa Bay and along the coast. Areas with low total value show a lack of data sets that have qualifiers falling within the ideal range, as per experts?? opinions. The gap maps created for this project are useful to identify priority areas where money should be invested for future data collection.     

Pollution indices as useful tools for the comprehensive evaluation of the degree of soil contamination–A review

The paper provides a complex, critical assessment of heavy metal soil pollution using different indices. Pollution indices are widely considered a useful tool for the comprehensive evaluation of the degree of contamination. Moreover, they can have a great importance in the assessment of soil quality and the prediction of future ecosystem sustainability, especially in the case of farmlands. Eighteen indices previously described by several authors (I_geo, PI, EF, C_f, PI_sum, PI_Nemerow, PLI, PI_ave, PI_Vector, PIN, MEC, CSI, MERMQ, C_deg, RI, mCd and ExF) as well as the newly published Biogeochemical Index (BGI) were compared. The content, as determined by other authors, of the most widely investigated heavy metals (Cd, Pb and Zn) in farmland, forest and urban soils was used as a database for the calculation of all of the presented indices, and this shows, based on statistical methods, the similarities and differences between them. The indices were initially divided into two groups: individual and complex. In order to achieve a more precise classification, our study attempted to further split indices based on their purpose and method of calculation. The strengths and weaknesses of each index were assessed; in addition, a comprehensive method for pollution index choice is presented, in order to best interpret pollution in different soils (farmland, forest and urban). This critical review also contains an evaluation of various geochemical backgrounds (GBs) used in heavy metal soil pollution assessments. The authors propose a comprehensive method in order to assess soil quality, based on the application of local and reference GB.     

Dynamics of grass–clover mixtures—An analysis of the response to management with the PROductive GRASsland Simulator (PROGRASS)

A dynamic plot-scale model PROGRASS was developed to simulate the seasonal and inter-annual dynamics of productive, cut grass/clover mixtures in response to management, and specifically to examine the role of root development on grass/clover interactions. The model was parameterized by virtue of data for dry matter yield, leaf area index, root mass, soil mineral N uptake and biological N fixation from a long-term field trial in north-eastern Switzerland. It was tested using 5 years of independent data for yield and clover fraction from a field experiment with two management regimes carried out on the Swiss Central Plateau. The results of transient simulations indicated that under intensive fertilization grass dominance was initiated by preferential allocation of assimilates to the roots. The rapid growth of the grass root system lowered the substrate C:N ratio, favouring carbon allocation to the shoot, which eventually provided competitive advantages with respect to light interception. Under extensive management, limited N acquisition capacity of the grass root system maintained preferential allocation to the roots, limiting shoot development in the grass and leading to clover dominance. Co-existence regimes with dominance by one of the components were also found in equilibrium experiments, with a transition regime from clover to grass dominance for annual N applications in the range 100–200 kg N ha⁻¹ y⁻¹ that reflected adjustments of the root system to fertilization. It is concluded that the dynamics of grass/clover mixtures is driven by negative and positive feedbacks in the soil–plant system that are strongly controlled by root development and therefore by the allocation patterns of the grass component.     

Quaternary phosphonium cationic ionic liquid/porous metal–organic framework as an efficient catalytic system for cycloaddition of carbon dioxide into cyclic carbonates

Environmental Chemistry Letters - Global warming and climate change concerns are triggering worldwide interest for sustainable transformation of CO2 into useful chemicals. Here, a new and efficient...     

Assessing the impact of biological control of Plutella xylostella through the application of Lotka–Volterra model

The Lotka–Volterra model was applied to the population densities of diamondback moth (DBM), Plutella xylostella (L.) and its exotic larval parasitoid Diadegma semiclausum (Hellen) data that was collected earlier by icipe's DBM biological control team. The collections were done for 15 months before the release and 36 months after release of the parasitoid in two areas; in Werugha, Coast Province of Kenya and Tharuni, Central Province of Kenya, respectively. For each area in pre- and post-release periods, we estimated Lotka–Volterra model parameters from the minimization of the loss function between the theoretical and experimental time-series datasets following the Nelder-Mead multidimensional method. The model estimated a reduction in the value of the steady state of DBM population from 4.86 to 2.17 in Werugha and from 6.11 to 3.76 and 3.45 (with and without exclusion of the time before D. semiclausum recovery) in Tharuni when transiting from the pre- and post-release periods, respectively. This change was a consequence of the newly introduced parasitoid, in the areas. The study presented a successful and detailed technique for non-linear model parameters restoration which was demonstrated by the correct mimicking of empirical datasets from the classical biological control with D. semiclausum, in different areas of Kenya. The applied model has measured the parasitoids impact on the DBM biological control through a quantitative estimate of the effectiveness of the newly introduced species D. semiclausum. These equations may therefore be used as tool for decision making in the implementation for such pests’ management system strategy.     

Mitochondrial DNA evidence for rapid colonisation of the Indo–West Pacific by the mudcrab Scylla serrata

Scylla serrata (Forskål, 1775) is widely distributed throughout mangrove habitats of the Indo-West Pacific (IWP) coastal waters. This study investigated the phylogeographic distribution of S. serrata mitochondrial DNA haplotypes sampled throughout the species range. Adults were sampled from three west Indian Ocean locations (N?=?21), five west Pacific sites (N?=?28) and three sites from northern and eastern Australia (N?=?76). Temperature-gradient gel-electrophoresis and sequencing of 549 base pairs of a mtDNA gene (cytochrome oxidase 1) identified 18 distinct haplotypes. Haplotypes cluster into two clades separated by ?2% sequence-divergence. One clade is widespread throughout the IWP, the other is strictly confined to northern Australia. Genealogical assessment of sequenced haplotypes suggests that the historical spread of S. serrata throughout the IWP has occurred rapidly and recently (<1 million years before present) from a west Pacific origin. The fact that many locations contain a single unique haplotype suggests limited contemporary gene flow between trans-oceanic sites, and that recent historical episodes of population founding and retraction have both determined and affected the current distribution of S. serrata populations. Contrary to that reported for other widespread species of IWP taxa, there is no pattern of regional separation of Indian from Pacific Ocean populations. However, results do suggest a vicariant separation of northern Australian crabs prior to the IWP radiation. We speculate that this separation may have resulted in the formation of a new species of Scylla.     

Rapid synthesis of mono/bimetallic (Zn/Co/Zn–Co) zeolitic imidazolate frameworks at room temperature and evolution of their CO2 uptake capacity

Environmental Chemistry Letters - Carbon dioxide (CO2) emissions from fossil fuels cause air pollution and lead to adverse impact on environment. To achieve low-carbon economy, capturing CO2 in the...