Solid phase extraction of Cu (II), Ni (II), Co (II), and Fe (III) ions in water samples using salicylaldehyde benzoylhydrazone on Amberlite XAD-4 and their determinations by flame atomic absorption spectrometry

A multi element preconcentration procedure for solid phase extraction on Amberlite XAD-4 as their salicylaldehyde benzoylhydrazone chelates and flame atomic absorption spectrometric determination of some trace metal ions in water samples are proposed in this work. The influences of some analytical parameters, including pH of aqueous solution, amounts of reagent, flow rates of sample and eluent solutions, and sample volume on the quantitative recoveries of copper, nickel, cobalt, and iron were investigated. The effects of concomitant ions on the retentions of the analytes were also examined. The developed method has been successfully applied to the determination of metal ions in some real samples, including, tap water, river water, spring water, and waste water.     

Exploring community assembly through an individual-based model for trophic interactions

Traditionally, the dynamics of community assembly has been analyzed by means of deterministic models of differential equations. Despite the theoretical advances provided by such models, they are restricted to questions about community-wide features. The individual-based modeling offers an opportunity to link bionomic features to patterns at the community scale, allowing us to understand how trait-based assembly rules can arise by dynamical processes. The present paper introduces an individual-based model of community assembly, and discusses some of the major advantages and drawbacks of this approach. The model was framed to deal with predation among size-structured populations, incorporating allometric constraints to energetic requirements, movement, life-history features and interaction relationships among individuals. A protocol of assembly procedure is proposed, in which a period of intense species introductions is followed by a period without introductions. The resultant communities did not present any pattern of trait over-dispersion, meaning that the multivariate distances of bionomic features among co-occurring species were neither larger nor more regular than expected in a random collection of species. It suggests a weak influence of interspecific interactions in the model environment and individualistic rules of coexistence, driven mainly by the spatial structure. This highlights that trait over-dispersion and resource partitioning should not be considered a necessary condition for coexistence, even in communities entirely structured by internal processes like predation and competition.     

Health hazards from exposure to cobalt with special reference to carcinogenic,mutagenic and teratogenic effects†

Occupational exposure to cobalt‐containing dust may cause a severe type of pneumoconiosis as well as obstructive lung disease. Peroral exposure to cobalt chloride may under certain circumstances precipitate cardiomyopathy.

There are only a limited number of experimental studies available which deal with the carcinogenic, mutagenic and teratogenic effects of cobalt and its salts. Single or repeated injections of cobalt powder or cobalt chloride have been shown to induce malignant tumours at the site of injection in rats, but not in mice. In vitro studies have shown that cobalt chloride has mutagenic and teratogenic properties. There are no data available on cancer incidence among workers occupationally exposed to cobalt. Thus the possible role of cobalt in human carcinogenesis is still an open question.     

The chemical form of cobalt-60 in the marine sponge Spirastrella cuspidifera

The marine sponge Spirastrella cuspidifera Lamarck shows a remarkable capacity to concentrate cobalt-60 from its environment, the specific activity of the radionuclide being two orders of magnitude higher than that in the ambient water. This suggests a very slow equilibrium with stable cobalt. The chemical form of the deposited cobalt-60 has been investigated in S. cuspidifera collected from coastal waters in the vicinity of a nuclear power station. The majority of the cobalt-60, 75 to 85%, is readily extractable into distilled water. Chromatographic analysis of this soluble fraction shows that about 85% of the cobalt is present as a small-molecular weight complex of low stability. No binding to any specific protein could be identified. The possible mechanism for the preferential uptake of cobalt-60 by this species of sponge is discussed.     

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.     

分析样品处理中的红外线快速加热技术

本文研究了红外线快速加热样品处理工艺,红外线由钨灯产生,酸性悬浊液样品盛在玻璃容器中.该工艺的主要优点是结构简单、费用低.另外,稀酸溶液不到60s中就可加热到需要温度,且整个过程不到5min.该工艺适用于痕量分析,最初的研究是测定牛肝、苹果叶等原料中的Cu、Fe、Mn含量.结果可以达到95%的置信水平.在未经任何预处理或仅做冷冻干燥情况下,可测定铜和锰的含量,证实与用常规的微波辅助法结果一致.     

Analysis of heavy metals in ecstasy tablets by electrochemical methods

Trace amounts of heavy metals have been analysed by electrochemical techniques in ecstasy tablets obtained from different police seizures in Spain. Lead, cadmium, copper and zinc were determined by differential-pulse anodic stripping voltammetry at a hanging mercury drop electrode, whereas nickel and cobalt were determined by adsorptive differential-pulse cathodic stripping voltammetry from their dimethylglyoxime complexes, M(DMG)₂. The performance of the procedure was compared with electrothermal atomic absorption spectrometry. The procedure was applied to the determination of these elements in nine ecstasy samples, finding that Zn is the element present in the highest concentration, ranging from 0.3 to 200?mg?kg^?1, Ni, Cu appear below 15?mg?kg^?1 and Pb below 8?mg?kg^?1, while Cd and Co levels were always lower than 0.51?mg?kg^?1.     

Spectrophotometry determination of Congo red in river water samples using nanosilver

A spectrophotometric procedure for the anionic diazo dye Congo red was proposed based on nanosilver catalyzed oxidation by potassium iodate in a hydrochloric acid medium. The calibration graph is linear for 0.8–240?mg?L^?1, and the detection limit is 0.6?mg?L^?1. Most foreign ions do not interfere with the determination, except for Cu(II), Fe(III), and Cr(VI). The interferences of Cu(II) and Fe(III) could be eliminated by masking with ethylene diamine tetraacetate, and that of Cr(VI) by reducing to Cr(III) with ascorbic acid. The typical features of this procedure are that it is sensitive for Congo red, and the determination could be carried out at room temperature. It had been used for the determination of Congo red in the Ganjnameh river water sample.     

Determination trace amounts of copper, nickel, cobalt and manganese ions in water samples after simultaneous separation and preconcentration

In the present article, a simple, rapid, sensitive and economical method has been developed for the simultaneous separation and preconcentration of the trace amounts of copper, nickel, cobalt and manganese in water samples by using modified XAD-4 resins. The sorption was quantitative in the pH range 6.0–9.0, whereas quantitative desorption occurred instantaneously with 5.0 mL of 2 M HNO₃, and selected elements have been determined by using flame atomic absorption spectrometry. Dynamic ranges were 0.04–3.5, 0.1–6.0, 0.04–4.5 and 0.04–4.0 μg/mL for copper, nickel, cobalt and manganese, respectively. The detection limits were 9.2, 28.6, 12.3 and 5.7 ng/mL for Cu(II), Ni(II), Co(II) and Mn(II), respectively. The effects of the experimental parameters, including the sample pH, eluent type, interference ions and breakthrough volume, were studied for separation and preconcentration of Cu(II), Ni(II), Co(II) and Mn(II) ions. Determination of these ions in standard samples confirmed that the proposed method has good accuracy. The proposed method was used for the determination of these ions in water samples.     

Solving the probabilistic reserve selection problem

The Reserve Selection Problem consists in selecting certain sites among a set of potential sites for biodiversity protection. In many models of the literature, the species present and able to survive in each site are supposed to be known. Here, for every potential site and for every species considered, only the probability that the species survives in the site is supposed to be known. The problem to select, under a budgetary constraint, a set of sites which maximizes the expected number of species is known in the literature under the name of probabilistic reserve selection problem. In this article, this problem is studied with species weighting to deal differently with common species and rare species. A spatial constraint is also considered preventing to obtain too fragmented reserve networks. As in Polasky et al. (2000), the problem is formulated by a nonlinear mathematical program in Boolean variables. Camm et al. (2002) developed a mixed-integer linear programming approximation that may be solved with standard integer programming software. The method gives tight approximate solutions but does not allow to tell how far these solutions are from the optimum. In this paper, a slightly different approach is proposed to approximate the problem. The interesting aspect of the approach, which also uses only standard mixed-integer programming software, is that it leads, not only to an approximate solution, but also to an upper limit on the true optimal value. In other words, the method gives an approximate solution with a guarantee on its accuracy. The linear reformulation is based on an upper approximation of the logarithmic function by a piecewise-linear function. The approach is very effective on artificial instances that include up to 400 sites and 300 species. Within an average CPU time of about 12 min, near-optimal solutions are obtained with an average relative error, in comparison to the optimum, of less than 0.2%.     

Metal passivity as mechanism of metal carcinogenesis: Chromium,nickel, iron,copper, cobalt,platinum, molybdenum

For the transition metals chromium, nickel, iron, copper, cobalt, platinum, and molybdenum, mechanisms of stable bonding in biochemistry (emphasis on carcinogenic mechanisms), chemistry, industrial chemistry, as well as epidemiological, occupational, orthopedic (implant devices) effects related to carcinogenesis, were reviewed. Hypothetically, the propensity to stable bonding (inertness), which ensures the metals’ performance capacity for consumers and industrial application, relates to their carcinogenicity. For chromium, a relationship between industrial/chemical and biological reactivity was noted for the tendency of Cr(III) ions to cause hydrolysis previous to stable bonding, as occurs during anodic passivation, leather tanning, and as indicated in biochemical studies pertaining to a mechanism of DNA condensation, which was suggested as a carcinogenic mechanism. The involvement of metal hydrolysis in both anodic passivation and biochemistry was noted also for nickel, iron, and platinum; the DNA interaction of platinum (cis-platin) is known to depend on hydrolysis. For nickel, issues of potential (V) were found important in both passivation and carcinogenicity. Comparably, the passivity behavior of cobalt and copper was found atypical, and their carcinogenicity yet unclear. Molybdenum, contained in passivated metallic implants, may relate to implant-associated carcinogenesis. Occupational carcinogenic effects were indicated for chromium, nickel, iron, and cobalt as caused by both reactive and passivated metal species. Exposure to acids and chronic respiratory irritation/infection/inflammation in workers were important cofactors in metal carcinogenesis. For wood and leather workers exposed to dust, the assumed presence in dust of metal particles abraded from alloys (sawing or cutting blades) may be a carcinogenic exposure hazard.     

Determination of cobalt by air-assisted liquid–liquid microextraction

Abstract

A rapid and selective technique for extraction, preconcentration and determination of trace amounts of cobalt in water and pharmaceutical samples by air-assisted liquid–liquid microextraction combined with flame atomic absorption spectrometry is proposed. 1-Nitroso-2-naphthol is used as a complexing agent and 1-octanol as an extraction solvent. Parameters relevant for analytical effectivity, i.e. pH of sample solution, concentration of complexing agent, volume of extraction solvent, and number of extraction cycles are optimized using a Box–Behnken design. At optimum conditions, a dynamic linear range of 5–600?µg L^?1 is obtained, with a limit of detection of 1.2?µg L^?1. The method is used for determination of Co(II) in environmental water and pharmaceutical samples.     

Assessing the Value of the Umbrella‐Species Concept for Conservation Planning with Meta‐Analysis

Abstract: The umbrella‐species concept, which suggests that conservation strategies designed for one species may benefit co‐occurring species, has been promoted as a framework for conservation planning. Nevertheless, there has been considerable variation in the outcome of empirical tests of this concept that has led researchers to question its value, so we used data from 15 published studies in a meta‐analysis to evaluate whether conservation of putative umbrella species also conserves co‐occurring species. We tested the effectiveness of putative umbrella species categorized by taxonomic group, taxonomic similarity to co‐occurring species, body size, generality of resource use, and trophic level to evaluate criteria proposed to guide the selection of umbrella species. We compared species richness and number of individuals (by species and higher taxonomic group) between sites with and without putative umbrella species to test whether more co‐occurring species were present in greater abundances when the area or resource needs of umbrella species were met. Species richness and abundance of co‐occurring species were consistently higher in sites where umbrella species were present than where they were not and for conservation schemes with avian than with mammalian umbrella species. There were no differences in species richness or species abundance with resource generalist or specialist umbrella species or based on taxonomic similarity of umbrella and co‐occurring species. Taxonomic group abundance was higher in across‐taxonomic umbrella species schemes than when umbrella species were of the same taxon as co‐occurring species. Co‐occurring species had similar, or higher, species richness with small‐bodied umbrella species relative to larger‐bodied umbrella species. The only significant difference among umbrella species categorized by trophic level was that species richness was higher with omnivorous than it was with carnivorous avian umbrella species. Our results suggest there is merit to the umbrella‐species concept for conservation, but they do not support the use of the criteria we used to identify umbrella species.     

Reagenzienfreie Bestimmung von Quecksilberspuren in Wasserproben

A comprehensive ecological monitoring of hazardous substances is indispensable to preserve our health and environment. Therefore, fast and inexpensive techniques for routine analysis of pollutants are essential. However, in the measuring procedure itself often toxic reagents are used producing hazardous waste. Omitting environmentally hazardous substances in the analysis procedure is an important contribution to a more sustainable and green analytical chemistry. A reagent-free method for ultra-trace (pg to ng?L^-1) mercury determination in water samples was developed and validated. An active nanogold collector integrated in a fully automated flow injection system is the core of this new method. All mercury species dissolved in the water sample are adsorbed and preconcentrated on the nano-structured gold surface of the collector. After rinsing and drying of the collector, the enriched mercury is thermally desorbed and finally measured by atomic fluorescence spectrometry. This method was optimized and validated for the determination of mercury in natural waters. The influence of various water constituents was investigated and only high contents of dissolved organic carbon (DOC) showed interferences of mercury preconcentration due to the strong complexation of mercury by DOC. This restriction can be solved by UV-irradiation, i.?e. reagent-free digestion of DOC rich samples prior to the preconcentration procedure. Mercury concentration of several natural river and sea waters and water from the discharge of a waste water treatment plant were determined with this new analytical method. Accuracy and precision of the method were demonstrated by several recovery experiments in natural water samples (recoveries: 96–102?%) and by analysis of the certified reference material BCR-579 (Mercury in Coastal Sea Water; recovery: 101?±?1?%). With a detection limit of only 80?pg?Hg?L^–1 the proposed method is highly sensitive. Furthermore the method avoids potential contamination of the sample by reagent addition and is due to the reagent-free procedure environment-friendly. Hence this work is an important contribution to sustainable environmental analysis and at the same time improves accurate routine mercury trace analysis.     

天然湖水表面微层砷,磷酸盐,悬浮颗粒物及藻类富集现象的研究

本文利用自制的玻璃板表面微层水采样器采集并分析了天津水上公园湖水表面微层中砷的四种不同形态：亚砷酸盐、砷酸盐、一甲基刖酸盐、二甲基刖酸盐，以及溶解态总磷、总磷、县浮颗粒物和藻类的富集情况，初步探讨了它们在湖水表面微层富集的原因，结果表明，它们在湖水表面微层中均有不同程度的富集现象，其中以总磷、悬浮颗粒物和藻类尤为明显，它们在湖水表面微层的富集除了也大气物理运动过程的生物活动有关外，还与采样站位有关     

Catalytic determination of ultratrace chromium based on gallocyanine‐hydrogen peroxide indicator reaction

A highly sensitive catalytic procedure for the determination of ultratrace chromium(VI) was developed based on its catalytic effect on the oxidation of gallocyanine by hydrogen peroxide in hexamine‐hydrochloric acid buffer solution. The reaction was followed spectrophotometrically by measuring the rate of change in the absorbance at 620 nm. The apparent active energy of the catalytic reaction is 6.84 kJ . mol^‐1. The calibration graph is linear for 0–150 ng.ml^‐1, and the detection limit is 0.8 ng.ml^‐1. Most foreign ions have no interfering effect on the determination of chromium(VI) except for Al³⁺, Cu²⁺, Fe³⁺and Fe²⁺. The interference of Al³⁺ is eliminated by masking with F^‐, and those of Cu²⁺, Fe³⁺ and Fe²⁺ are eliminated by adding appropriate amount of EDTA. The present procedure had been used for the determination of trace chromium(VI) in lake water, mine water and electroplating wastewater, and the results were satisfactory.     

Determination of phenol,cresols and xylenols in workplace air using XAD‐2 sorbent cartridges

A method for sampling and analysis of phenolic compounds in workplace atmospheres using Amberlite XAD‐2 sorbent tubes has been laboratory and field tested. After extraction of the adsorbed phenols with methylene chloride, the concentrated extract was analyzed by capillary column gas chromatography coupled with a flame ionization detector or a mass spectrometer. For a 3L air sample, the method has a detection limit for phenol, cresols, alkyl‐substituted phenols and xylenols of 0.3 mg/m³ using gas chromatography with flame ionization detection (GC/FID) analysis and 0.07 mg/m³ using gas chromatography mass spectroscopy/selected ion monitoring GC‐MS/SIM. Evaluation tests conducted in the laboratory indicated recoveries >85% for a wide range of phenols, cresols, xylenols and other alkyl‐substituted phenols and resorcinol. Sampling conditions were established to ensure that no breakthrough occurred for a predetermined sample volume of three (3) liters even in humid atmospheres. Stability tests indicated that for storage of up to 2 weeks at 4°C, only resorcinol showed a significant reduction in sample recovery. The proposed method and NIOSH Method 3502 were compared for the determination of phenol concentrations in air samples collected at a plant processing phenolic resins. Phenol was positively identified in the XAD sample using GC‐MS/SIM and was detected at concentrations of 40–50% of the total phenols detected using NIOSH Method 3502. This difference is attributed to the airborne paniculate matter which is known to contain bisphenols that will contribute to the total phenolic content sampled in Method 3502, but not on the XAD sample.     

Nonparametric estimation of Shannon’s index of diversity when there are unseen species in sample

A biological community usually has a large number of species with relatively small abundances. When a random sample of individuals is selected and each individual is classified according to species identity, some rare species may not be discovered. This paper is concerned with the estimation of Shannons index of diversity when the number of species and the species abundances are unknown. The traditional estimator that ignores the missing species underestimates when there is a non-negligible number of unseen species. We provide a different approach based on unequal probability sampling theory because species have different probabilities of being discovered in the sample. No parametric forms are assumed for the species abundances. The proposed estimation procedure combines the Horvitz–Thompson (1952) adjustment for missing species and the concept of sample coverage, which is used to properly estimate the relative abundances of species discovered in the sample. Simulation results show that the proposed estimator works well under various abundance models even when a relatively large fraction of the species is missing. Three real data sets, two from biology and the other one from numismatics, are given for illustration.     

Shell preference in a hermit crab: comparison between a matrix of paired comparisons and a multiple-alternative experiment

The preference of the hermit crab, Calcinus californiensis, among six species of shells, was tested by two different experiments. The first experiment used pair-wise trials, analyzing the preference by Chi-square tests using two different constructions of the null hypothesis. One hypothesis was based on a no-preference among shell species, the second on comparing the number of crabs changing for a particular shell species when two options were given versus the changing when no options were offered. The second experiment was a multiple-alternative test based on a rank ordering of the shell preference. This method has both statistical and resource-saving advantages over the traditional pair-wise comparisons. The sequence of shell preference was similarly independent of the procedure used. The preferred shell species are heavy and might be associated with hydrodynamic advantages and with the protection against predation. The shell preference matches with the pattern of shell occupancy indicating that the shell use in nature is determined by the crab’s preference. The information generated may be used for further research on shell preference as a methodological alternative.