Unsupervised genetic algorithm deployed for intrusion detection

This paper represents the first step in an on-going work for designing an unsupervised method based on genetic algorithm for intrusion detection. Its main role in a broader system is to notify of an unusual traffic and in that way provide the possibility of detecting unknown attacks. Most of the machine-learning techniques deployed for intrusion detection are supervised as these techniques are generally more accurate, but this implies the need of labeling the data for training and testing which is time-consuming and error-prone. Hence, our goal is to devise an anomaly detector which would be unsupervised, but at the same time robust and accurate. Genetic algorithms are robust and able to avoid getting stuck in local optima, unlike the rest of clustering techniques. The model is verified on KDD99 benchmark dataset, generating a solution competitive with the solutions of the state-of-the-art which demonstrates high possibilities of the proposed method.

Design and evaluation of intelligent classifier based intrusion detection system

We have discovered a novel approach of intrusion detection system using an intelligent data classifier based on a self organizing map (SOM). We have surveyed all other unsupervised intrusion detection methods, different alternative SOM based techniques and KDD winner IDS methods. This paper provides a robust designed and implemented intelligent data classifier technique based on a single large size (30x30) self organizing map (SOM) having the capability to detect all types of attacks given in the DARPA Archive 1999 the lowest false positive rate being 0.04 % and higher detection rate being 99.73% tested using full KDD data sets and 89.54% comparable detection rate and 0.18% lowest false positive rate tested using corrected data sets.

The polychaete worm Nereis diversicolor increases mercury lability and methylation in intertidal mudflats

The polychaete worm Nereis diversicolor engineers its environment by creating oxygenated burrows in anoxic intertidal sediments. The authors carried out a laboratory microcosm experiment to test the impact of polychaete burrowing and feeding activity on the lability and methylation of mercury in sediments from the Bay of Fundy, Canada. The concentration of labile inorganic mercury and methylmercury in burrow walls was elevated compared to worm-free sediments. Mucus secretions and organic detritus in worm burrows increased labile mercury concentrations. Worms decreased sulfide concentrations, which increased Hg bioavailability to sulfate-reducing bacteria and increased methylmercury concentrations in burrow linings. Because the walls of polychaete burrows have a greater interaction with organisms, and the overlying water, the concentrations of mercury and methylmercury they contain is more toxicologically relevant to the base of a coastal food web than bulk samples. The authors recommend that researchers examining Hg in marine environments account for sediment dwelling invertebrate activity to more fully assess mercury bioavailability.

Mercury and methylmercury bioaccumulation by polychaete worms is governed by both feeding ecology and mercury bioavailability in coastal mudflats

Polychaete worms are abundant in many mudflats but their importance to coastal food web Hg biomagnification is not known. We sampled sediments and polychaete worms from mudflats in the Bay of Fundy to investigate the bioaccumulation of mercury (Hg) and methylmercury (MeHg) in the coastal invertebrate food web. Hg concentrations in the sediments were low (<20 μg kg−1). Labile Hg (methanol/KOH sediment extraction) in surface sediments (0–1 cm) was positively correlated with Hg bioaccumulation by surface sediment-ingesting polychaetes but, surprisingly, there was a negative correlation between δ15N (i.e. trophic level) and THg bioaccumulation factors in polychaete worms. Worms feeding on deeper sediments contained the greatest MeHg concentrations (69.6 μg kg−1). Polychaetes are an important vector for Hg biomagnification to the coastal avian food web. This research demonstrates that feeding depth and method of feeding are more important than trophic position or sediment Hg concentrations for predicting Hg bioaccumulation.

Modeling the photo-oxidation of dissolved organic matter by ultraviolet radiation in freshwater lakes: implications for mercury bioavailability

Uncertainties in projected ultraviolet (UV) radiation may lead to future increases in UV irradiation of freshwater lakes. Because dissolved organic carbon (DOC) is the main binding phase for mercury (Hg) in freshwater lakes, an increase in DOC photo-oxidation may affect Hg speciation and bioavailability. We quantified the effect of DOC concentration on the rate of abiotic DOC photo-oxidation for five lakes (DOC = 3.27–12.3 mg L−1) in Kejimkujik National Park, Canada. Samples were irradiated with UV-A or UV-B radiation over a 72-h period. UV-B radiation was found to be 2.36 times more efficient at photo-oxidizing DOC than UV-A, with energy-normalized rates of dissolved inorganic carbon (DIC) production ranging from 3.8 × 10−5 to 1.1 × 10−4 mg L−1 J−1 for UV-A, and from 6.0 × 10−5 to 3.1 × 10−4 mg L−1 J−1 for UV-B. Energy normalized rates of DIC production were positively correlated with DOC concentrations. Diffuse integrated attenuation coefficients were quantified in situ (UV-A Kd = 0.056–0.180 J cm−1; UV-B Kd = 0.015–0.165 J cm−1) and a quantitative depth-integrated model for yearly DIC photo-production in each lake was developed. The model predicts that, UV-A produces between 3.2 and 100 times more DIC (1521–2851 mg m−2 year−1) than UV-B radiation (29.17–746.7 mg m−2 year−1). Future increases in UV radiation may increase DIC production and increase Hg bioavailability in low DOC lakes to a greater extent than in high DOC lakes.

Effects of coastal managed retreat on mercury biogeochemistry

We investigated the impact of managed retreat on mercury (Hg) biogeochemistry at a site subject to diffuse contamination with Hg. We collected sediment cores from an area of land behind a dyke one year before and one year after it was intentionally breached. These sediments were compared to those of an adjacent mudflat and a salt marsh. The concentration of total mercury (THg) in the sediment doubled after the dyke was breached due to the deposition of fresh sediment that had a smaller particle size, and higher pH. The concentration of methylmercury (MeHg) was 27% lower in the sediments after the dyke was breached. We conclude that coastal flooding during managed retreat of coastal flood defences at this site has not increased the risk of Hg methylation or bioavailability during the first year. As the sediment becomes vegetated, increased activity of Hg-methylating bacteria may accelerate Hg-methylation rate.

An event of stratospheric air intrusion and its associated secondary surface cyclogenesis over the South Atlantic Ocean

This work presents an analysis of a lowermost stratospheric air intrusion event over the coast of Brazil, which may have been responsible for a secondary surface cyclogenesis over the southwestern Atlantic Ocean. The surface cyclone initiated at 0600 UTC 17 April 1999 in a cold air mass in the rear of a cold front after a primary cyclone developed over the same region. The analysis of the secondary cyclone revealed the presence of lowermost stratospheric air intrusion characterized by anomalous potential vorticity (PV), dry air, and high concentration of ozone in atmospheric column. The system developed on the eastern side of an upper level core of PV anomaly, which induced a cyclonic wind circulation at lower levels and favored the onset of the secondary cyclone. In midlevels (500 hPa), the cutoff low development contributed to reduce the propagation speed of the wave pattern. This feature seemed to (1) allow the low-level cold/dry air to heat/moisten associated with sensible and latent fluxes transferred from the ocean to the atmosphere, which intensified a baroclinic zone parallel to the coast, and (2) contribute to the long duration of the system. The present analysis indicates that this secondary cyclone development could be the result of the coupling between the PV anomaly in the upper levels and low-level air-sea interaction.

Calixarene and Resorcarene Based Receptors: From Structural and Thermodynamic Studies to the Synthesis of a New Mercury(II) Selective Material

Materials used in current technological approaches for the removal of mercury lack selectivity. Given that this is one of the main features of supramolecular chemistry, receptors based on calix[4]arene and calix[4]resorcarene containing functional groups able to interact selectively with polluting ions while discriminating against biologically essential ones were designed. Thus two receptors, a partially functionalized calix[4]arene derivative, namely, 5,11,17,23-tetra-tert-butyl [25-27-bis(diethyl thiophosphate amino)dihydroxy] calix[4]arene (1) and a fully functionalized calix[4]resorcarene, 4,6,10,12,16,18,22,24-diethyl thiophosphate calix[4]resorcarene (2) are introduced. Mercury(II) was the identified target due to the environmental and health problems associated with its presence in water Thus following the synthesis and characterization of 1 and 2 in solution ((1)HNMR) and in the solid state (X-ray crystallography) the sequence of experimental events leading to cation complexation studies in acetonitrile and methanol ((1)H NMR, conductance, potentiometric, and calorimetric measurements) with the aim of assessing their behavior as mercury selective receptors are described. The cation selectivity pattern observed in acetonitrile follows the sequence Hg(II) > Cu(II) > Ag(I). In methanol 1 is also selective for Hg(II) relative to Ag(I) but no interaction takes place between this receptor and Cu(II) in this solvent. Based on previous results and experimental facts shown in this paper, it is concluded that the complexation observed with Cu(II) in acetonitrile occurs through the acetonitrile-receptor adduct rather than through the free ligand. Receptor 2 has an enhanced capacity for uptaking Hg(II) but forms metalate complexes with Cu(II). These studies in solution guided the inmobilization of receptor 1 into a silica support to produce a new and recyclable material for the removal of Hg(II) from water. An assessment on its capacity to extract this cation from water relative to Cu(II) and Ag (I) shows that the cation selectivity pattern of the inmobilized receptor is the same as that observed for the free receptor in methanol. These findings demonstrate that fundamental studies play a critical role in the selection of the receptor to be attached to silicates as well as in the reaction medium used for the synthesis of the new decontaminating agent.

Columnar joints in the Patino Formation sandstones, Eastern Paraguay: a dynamic interaction between dyke intrusion, quartz dissolution and cooling-induced fractures

The Patino Formation sandstones, which crop out in Aregua neighborhood in Eastern Paraguay and show columnar joints near the contact zone with a nephelinite dyke, have as their main characteristics the high proportion of syntaxial quartz overgrowth and a porosity originated from different processes, initially by dissolution and later by partial filling and fracturing. Features like the presence of floating grains in the syntaxial cement, the transitional interpenetrative contact between the silica-rich cement and grains as well as the intense fracture porosity are strong indications that the cement has been formed by dissolution and reprecipitation of quartz from the framework under the effect of thermal expansion followed by rapid contraction. The increase of the silica-rich cement towards the dyke in association with the orthogonal disposition of the columns relative to dyke walls are indicative that the igneous body may represent the main heat source for the interstitial aqueous solutions previously existing in the sediments. At macroscopic scale, the increasing of internal tensions in the sandstones is responsible for the nucleation of polygons, leading to the individualization of prisms, which are interconnected by a system of joints, formed firstly on isotherm surfaces of low temperature and later on successive adjacent planes towards the dyke heat source.

Development of a sequential injection-square wave voltammetry method for determination of paraquat in water samples employing the hanging mercury drop electrode

This work describes the development and optimization of a sequential injection method to automate the determination of paraquat by square-wave voltammetry employing a hanging mercury drop electrode. Automation by sequential injection enhanced the sampling throughput, improving the sensitivity and precision of the measurements as a consequence of the highly reproducible and efficient conditions of mass transport of the analyte toward the electrode surface. For instance, 212 analyses can be made per hour if the sample/standard solution is prepared off-line and the sequential injection system is used just to inject the solution towards the flow cell. In-line sample conditioning reduces the sampling frequency to 44 h(-1). Experiments were performed in 0.10 M NaCl, which was the carrier solution, using a frequency of 200 Hz, a pulse height of 25 mV, a potential step of 2 mV, and a flow rate of 100 mu L s(-1). For a concentration range between 0.010 and 0.25 mg L(-1), the current (i(p), mu A) read at the potential corresponding to the peak maximum fitted the following linear equation with the paraquat concentration (mg L(-1)): ip = (-20.5 +/- 0.3) Cparaquat -(0.02 +/- 0.03). The limits of detection and quantification were 2.0 and 7.0 mu g L(-1), respectively. The accuracy of the method was evaluated by recovery studies using spiked water samples that were also analyzed by molecular absorption spectrophotometry after reduction of paraquat with sodium dithionite in an alkaline medium. No evidence of statistically significant differences between the two methods was observed at the 95% confidence level.

Evaluation of a carbon paste electrode modified with organofunctionalised SBA-15 nanostructured silica in the simultaneous determination of divalent lead, copper and mercury ions

The performance of a carbon paste electrode (CPE) modified with SBA-15 nanostructured silica organofunctionalised with 2-benzothiazolethiol in the simultaneous determination of Pb(II), Cu(II) and Hg(II) ions in natural water and sugar cane spirit (cachaca) is described. Pb(II), Cu(II) and Hg(II) were pre-concentrated on the surface of the modified electrode by complexing with 2-benzothiazolethiol and reduced at a negative potential (-0.80 V). Then the reduced products were oxidised by DPASV procedure. The fact that three stripping peaks appeared on the voltammograms at the potentials of -0.48 V (Pb2+), -0.03 V (Cu2+) and +0.36 V (Hg2+) in relation to the SCE, demonstrates the possibility of simultaneous determination of Pb2+, Cu2+ and Hg2+. The best results were obtained under the following optimised conditions: 100 mV pulse amplitude, 3 min accumulation time, 25 mV s(-1) scan rate in phosphate solution pH 3.0. Using such parameters, calibration graphs were linear in the concentration ranges of 3.00-70.0 x 10(-7) mol L-1 (Pb2+), 8.00-100.0 X 10(-7) mol L-1 (Cu2+) and 2.00-10.0 x 10(-6) mol L-1 (Hg2+). Detection limits of 4.0 x 10(-8) mol L-1 (Pb2+), 2.0 x 10(-7) mol L-1 (Cu2+) and 4.0 x 10(-7) mol L-1 (Hg2+) were obtained at the signal noise ratio (SNR) of 3. The results indicate that this electrode is sensitive and effective for simultaneous determination of Pb2+, Cu2+ and Hg2+ in the analysed samples. (C) 2008 Published by Elsevier B.V.