Assessments of Algal Toxicity and PBT Behaviour of Pesticides with No Eco-toxicological Data: Predictive Ability of QSA/(T)R Models.

In the present study, the effect of eight pesticides with no ecotoxicological data on the growth rate of Chlorella vulgaris was measured. The selected pesticides are acetochlor, acetamiprid, boscalid diphenamid, gibberellic acid, ioxynil, diclofop and 2,4,5-T. The algal toxicity (IC50 ) of boscalid could not be determined within its solubility limit. Acetamiprid, diphenamid and gibberellic acid revealed IC50 values>100 mg/L. Among the others, the order of 96-h IC50 of pesticides was found as acetochlor>ioxynil>diclofop>2,4,5-T. The IC50 values were also predicted by using four Quantitative Structure-Activity/(Toxicity) Relationship (QSA/(T)R) models selected from the literature. The predictions of the models provided by QSARINS-Chem module of QSARINS as well as those obtained in our previous studies were compared with the results of experimental algal toxicity tests that were performed in our laboratory. The QSTR model generated for the toxicity of diverse chemicals to freshwater algae was able to correctly predict the toxicity order of the pesticides tested in the present study, confirming the utility of the QSA/(T)R approach. Additionally, Persistence, Bioaccumulation and Toxicity (PBT) Index model provided via the software QSARINS was employed and boscalid and diclofop were found to be PBT chemicals based on the PBT model. The present study will be very helpful when a more holistic approach applied to understand the fate of these chemicals in the environment.

Desulfitobacterium contributes to the microbial transformation of 2,4,5-T by methanogenic enrichment cultures from a Vietnamese active landfill.

The herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) was a major component of Agent Orange, which was used as a defoliant in the Vietnam War. Little is known about its degradation under anoxic conditions. Established enrichment cultures using soil from an Agent Orange bioremediation plant in southern Vietnam with pyruvate as potential electron donor and carbon source were shown to degrade 2,4,5-T via ether cleavage to 2,4,5-trichlorophenol (2,4,5-TCP), which was further dechlorinated to 3,4-dichlorophenol. Pyruvate was initially fermented to hydrogen, acetate and propionate. Hydrogen was then used as the direct electron donor for ether cleavage of 2,4,5-T and subsequent dechlorination of 2,4,5-TCP. 16S rRNA gene amplicon sequencing indicated the presence of bacteria and archaea mainly belonging to the Firmicutes, Bacteroidetes, Spirochaetes, Chloroflexi and Euryarchaeota. Desulfitobacterium hafniense was identified as the dechlorinating bacterium. Metaproteomics of the enrichment culture indicated higher protein abundances of 60 protein groups in the presence of 2,4,5-T. A reductive dehalogenase related to RdhA3 of D. hafniense showed the highest fold change, supporting its function in reductive dehalogenation of 2,4,5-TCP. Despite an ether-cleaving enzyme not being detected, the inhibition of ether cleavage but not of dechlorination, by 2-bromoethane sulphonate, suggested that the two reactions are catalysed by different organisms.

Toxic Epidemics: Agent Orange Sickness in Vietnam and the United States.

Social scientists studying toxic epidemics have often endeavored to shed light on the differences between scientists' and nonscientists' epistemic perspectives. Yet, little attention has been paid to the processes through which a toxic epidemic emerges as a phenomenon. A Luoi Valley of Central Vietnam was extensively sprayed with chemical defoliants (including Agent Orange) during the Vietnam War. The latent toxic effects of these chemicals, however, went largely unnoticed until the late 1990s. By juxtaposing the history through which the notion of "Agent Orange Sickness" emerged in the United States with an ethnographic study of A Luoi, I explore the notion of poison under which Agent Orange became recognizable as a poison.

Adsorption and photodegradation kinetics of herbicide 2,4,5-trichlorophenoxyacetic acid with MgFeTi layered double hydroxides.

The calcined layered double hydroxides (cLDHs) Ti-doped and undoped MgFe for this study were prepared by co-precipitation method followed by calcination at 500 °C. The as-prepared samples were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Brunauer Emmett Teller (BET) and UV-Vis diffuse reflectance spectrum (DRS) techniques and tested for adsorption and photodegradation (including photocatalytic and photo-Fenton-like) of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous solutions under visible light irradiation. In the range of studied operating conditions, the as-prepared samples exhibited excellent photo-Fenton-like activity, leading to more than 80-95% degradation of 2,4,5-T at initial concentration of 100 mg L(-1) with 4 g calcined LDHs per liter, was accomplished in 360 min, while 2,4,5-T half-life time was as short as 99-182 min. The kinetics of adsorption and photodegradation of 2,4,5-T were also discussed. These results offered a green, low cost and high efficiency photocatalyst for environmental remediation.

Agent Orange Exposure and 2,3,7,8-Tetrachlorodibenzo-p-Dioxin (TCDD) in Human Milk.

Agent Orange was sprayed in parts of southern Vietnam during the U.S.-Vietnam war and was a mixture of two chlorophenoxy herbicides. The mixture was contaminated with 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). TCDD and other dioxins and furans are measurable in the milk of Vietnamese women. We explored whether the TCDD in milk from these women was from Agent Orange and whether lactational exposure can be a mode of transgenerational effects of TCDD from Agent Orange. A review of the world's literature on milk concentrations of polychlorinated compounds showed the presence of TCDD and other dioxins and furans in all countries that have been assessed. The congener profile of these chemicals, that is, the proportion of different congeners in the sample, can be used to assess the source of milk contamination. Measurements in most countries, including contemporary measurements in Vietnam, are consistent with non-Agent Orange exposure sources, including industrial activities and incineration of waste. Models and supporting human data suggest that TCDD from breastfeeding does not persist in a child past adolescence and that the adult body burden of TCDD is independent of whether the individual was breast- or bottle-fed as a child. These findings suggest that exposure to Agent Orange in Vietnam did not result in persistent transgenerational exposure through human milk.

Electrochemical oxidation of 2,4,5-trichlorophenoxyacetic acid by metal-oxide-coated Ti electrodes.

Electrochemical oxidation of 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) over metal-oxide-coated Ti anodes, i.e., Ti/SnO2-Sb/Ce-PbO2, Ti/SnO2-Sb and Ti/RuO2, was examined. The degradation efficiency of over 90% was attained at 20 min at different initial concentrations (0.5-20 mg L(-1)) and initial pH values (3.1-11.2). The degradation efficiencies of 2,4,5-T on Ti/SnO2-Sb/Ce-PbO2, Ti/SnO2-Sb and Ti/RuO2 anodes were higher than 99.9%, 97.2% and 91.5% at 30 min, respectively, and the respective total organic carbon removal ratios were 65.7%, 54.6% and 37.2%. The electrochemical degradation of 2,4,5-T in aqueous solution followed pseudo-first-order kinetics. The compounds, i.e., 2,5-dichlorohydroquinone and 2,5-dihydroxy-p-benzoquinone, have been identified as the main aromatic intermediates by liquid chromatography-mass spectrometry. The results showed that the energy efficiencies of 2,4,5-T (20 mg L(-1)) degradation with Ti/SnO2-Sb/Ce-PbO2 anode at the optimal current densities from 2 to 16 mA cm(-2) ranged from 8.21 to 18.73 kWh m(-3).

Vibrational spectroscopic [FT-IR, FT-Raman] investigation on (2,4,5-Trichlorophenoxy) Acetic acid using computational [HF and DFT] analysis.

In the present methodical study, FT-IR, FT-Raman and NMR spectra of the (2,4,5-Trichlorophenoxy) Acetic acid are recorded. The observed fundamental frequencies (IR and Raman) are assigned according to their distinctiveness region. The hybrid computational calculations are carried out by HF and DFT (B3LYP and B3PW91) methods with 6-31++G(d,p) and 6-311++G(d,p) basis sets and the corresponding results are tabulated. The impact of the presence of tri-chlorine atoms in phenyl structure of the compound is investigated. The vibrational sequence pattern of the molecule related to CH2COOH is analyzed. Moreover, (13)C NMR and (1)H NMR are calculated by using the gauge independent atomic orbital (GIAO) method with B3LYP methods and the 6-311++G(d,p) basis set and their spectra are simulated and the chemical shifts related to TMS are compared. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, are performed by HF and DFT methods. The Kubo gap of the present compound is calculated related to HOMO and LUMO energies which confirm the occurring of charge transformation between the base and ligand group. Besides frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) was performed. NLO properties related to Polarizability and hyperpolarizability are also discussed.

High level of dioxin-TEQ in tissue is associated with Agent Orange exposure but not with biochemical recurrence after radical prostatectomy.

BACKGROUND: Agent Orange (AO) was previously identified as a significant risk factor for biochemical recurrence (BCR) after radical prostatectomy (RP) in prostate cancer patients. In this study, we determined the levels of dioxin biological toxicity using toxic equivalency (TEQ) values and examined the impact of dioxin-TEQ level on BCR. METHODS: A total of 93 men who underwent RP, with a median of 5.3 years of postoperative follow-up, were included in the study. The dioxin-TEQ level of each patient was measured using intraoperatively harvested abdominal subcutaneous fat. The dichotomous categorization of dioxin-TEQ by the 50th percentile (low<50% vs high 50%) was also used to regroup the patient cohort, regardless of the previous history of AO exposure. Comparisons between the dioxin-TEQ levels, clinicopathological characteristics and BCR in AO-exposed and -unexposed men were made to allocate possible risk factors. The multivariable logistic regression model was used to identify significant risk factors associated with BCR, adjusting for other confounding factors. RESULTS: The median dioxin-TEQ level in 37 AO-exposed patients was significantly higher than that in 56 unexposed patients (22.3 vs 15.0 pg g(-1) fat, respectively, P<0.001). The men with AO exposure were more likely to have a high dioxin-TEQ level (P<0.001). Neither AO exposure nor the level of dioxin-TEQ was associated with BCR. Tumor stage (T3/T4 vs T2) and Gleason grade (Gleason 3+4) were independent risk factors for BCR after RP. CONCLUSIONS: Exposure to AO significantly increases the adipose level of dioxin-TEQ in patients treated with RP. However, exposure to AO or a high dioxin-TEQ level was not associated with an increased risk of BCR after RP. This lack of association supports the current conclusion that the evidence of carcinogenicity of AO in prostate cancer patients is not sufficient and remains 'limited'.

A mechanistic study of the photodegradation of herbicide 2,4,5-trichlorophenoxyacetic acid in aqueous solution.

Photodegradation of herbicide 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) in aqueous solution was investigated by stationary (254 nm) and nanosecond laser (266 nm) flash photolysis techniques. It was shown that in the primary photochemical step both photoionization (which generates a hydrated electron-radical cation pair) and heterolytic cleavage of a C-Cl bond takes place. The major products of substitution of one of the chlorine atoms in the 2-, 4- or 5-position by a hydroxyl group as well as the products of hydroxylation of the benzene ring in 3- and 6-positions were identified by HPLC and LC-MS methods. The complexation of 2,4,5-T with ß- and γ-cyclodextrins (ß(γ)CD) was investigated. The influence of such complexation on the quantum yield of herbicide photolysis and on the ratio of photodegradation products was determined.

Degradation of 2,4,5-trichlorophenoxyacetic acid by a novel Electro-Fe(II)/Oxone process using iron sheet as the sacrificial anode.

A novel electrochemically enhanced advanced oxidation process for the destruction of organic contaminants in aqueous solution is reported in this study. The process involves the use of an iron (Fe) sheet as sacrificial anode and a graphite bar as cathode. In the oxidation process, once an electric current is applied between the anode and the cathode, a predetermined amount of Oxone is added to the reactor. Ferrous ions generated from the sacrificed Fe anode mediate the generation of highly powerful radicals (SO(4)(•-)) through the decomposition of Oxone. The coupled process of Fe(II)/Oxone and electrochemical treatment (Electro-Fe(II)/Oxone) was evaluated in terms of 2,4,5-Trichlorophenoxyacetic acid degradation in aqueous solution. Various parameters were investigated to optimize the process, including applied current, electrolyte and Oxone concentration. In addition, low solution pH facilitates the system performance due to the dual effects of weak Fenton reagent generation and persulfate ions generation, whereas the system performance was inhibited at basic pH levels through non-radical self-dissociation of Oxone and the formation of ferric hydroxide precipitates. Furthermore, the active radicals involved in the Electro-Fe(II)/Oxone process were also identified. The Electro-Fe(II)/Oxone process demonstrates a very high 2,4,5-T degradation efficiency (over 90% decay within 10 min), which justifies the novel Electro-Fe(II)/Oxone a promising treatment process for herbicide removal in water.

Characteristics of the abundance of polychlorinated dibenzo-p-dioxin and dibenzofurans, and dioxin-like polychlorinated biphenyls in sediment samples from selected Asian regions in Can Gio, Southern Vietnam and Osaka, Japan.

The levels of polychlorinated dibenzo-p-dioxin and dibenzofuran (PCDD/PCDFs), and dioxin-like polychlorinated biphenyls (DL-PCBs) were determined in sediment samples from Can Gio, South Vietnam, and Osaka, Japan. Can Gio is known for the defoliation of its mangrove forests by aerial spraying with Agent Orange during the Vietnam War, whereas Osaka is renowned for a PCDD/PCDF pollution accident at a municipal solid-waste incinerator. For comparison, we also analyzed PCDD/PCDFs and DL-PCBs in sediment samples from Hue and Hanoi, Vietnam. The toxic equivalent quantity (TEQ) values in Can Gio were as high as those in Hue, Hanoi, and suburban areas of Osaka, but much lower than those in urban areas of Osaka. The proportion of the World Health Organization (WHO)-TEQ value contributed by 2,3,7,8-tetrachlorinated dibenzo-p-dioxin (TCDD) in Can Gio was approximately 30%, higher than the values in the other sample areas. These data suggest that residual sedimentary TCDD that originated from aerial spraying of Agent Orange occur in only low concentrations in Can Gio. The main contributors to WHO-TEQ values in Can Gio are natural sources, as in Hue. In contrast, commercial PCBs are the dominant contributors to WHO-TEQ values in Hanoi. In Osaka, agrochemicals used in rice cultivation, the incineration of solid waste, and commercial PCBs equally contributed to WHO-TEQ values at suburban locations. The dumping of incinerator-related materials and/or the inadequate management of commercial PCBs have resulted in significantly elevated WHO-TEQ values of 240-370 ng kg(-1)dw at urban locations in Osaka.

Extraction and derivatization of polar herbicides for GC-MS analyses.

A sample preparation procedure including a simultaneous microwave-assisted (MA) extraction and derivatization for the determination of chlorophenoxy acids in soil samples is presented. For a selective and sensitive measurement, an analytical technique such as GC coupled with MS needs to be adopted. For GC analyses, chlorophenoxy acids have to be converted into more volatile and thermally stable derivatives. Derivatization by means of microwave radiation offers new alternatives in terms of shorter derivatization time and reduces susceptibility for the formation of artefacts. Extraction and derivatization into methyl esters (ME) were performed with sulphuric acid and methanol. Due to the novelty of the simultaneous extraction and derivatization assisted by means of microwave radiation, a careful investigation and optimization of influential reaction parameters was necessary. It could be shown that the combination of sulphuric acid and methanol provides a fast sample preparation including an efficient clean up procedure. The data obtained by the described method are in good agreement with those published for the reference material. Finally, compared to conventional heating and also to the standard procedure of the EPA, the sample preparation time could be considerably shortened.

Purification of seawater contaminated with undegradable aromatic ring compounds using ozonolysis followed by titanium dioxide treatment.

Treatment of aromatic ring compounds, 2,4-dichlorophenoxy acetic acid (2,4-D), 2,4,5-trichloro-phenoxy acetic acid (2,4,5-T), and bisphenol A, in the artificial seawater, i.e. Allen seawater, was carried out by ozonation and titanium dioxide (TiO2) photocatalyst treatment. Each compound was degraded and varnished within 30 min by only ozonolysis at pH 9.0 and at 20 degrees C, while the TOC value of each compound decreased gradually but reached almost constant value, i.e. about 70-80% of the initial value, at even 30 min of ozonation time. Ozonolysis (30 min of ozonation time) followed by TiO2 photocatalyst treatment (50h of reaction time) was a very effective method for decreasing the TOC values of aromatic ring compounds in the artificial seawater. In consequence, TOC values of 2,4-D, 2,4,5-T, and bisphenol A could be reduced to about 28, 21, and 34% of their initial values, respectively.

Colloid facilitated transport of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) to the groundwater at Ma Da area, Vietnam.

PCDD/Fs are hydrophobic organic substances and strongly sorbing to soil particles. Once adsorbed to soil particles they are believed to be virtually immobile. However, research in the last decades confirmed that strong sorbing contaminants may reach the groundwater via colloid-facilitated transport. This pathway has not been investigated before in Vietnam. Ma Da area, 100 km north of Ho Chi Minh City, was repeatedly sprayed during the Vietnam War (1962-1971) with herbicides like Agent Orange containing, beside others, the teratogenic contaminant 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD). 11 surface soil samples and 12 water samples were collected in Ma Da area for analysis of PCDD/Fs in solids. Soil TCDD concentrations ranged from 1-41 ppt with a mean of 8.8 ppt and a mean I-TEQ of 9.7 ppt. Two surface water samples showed colloid bound TCDD (7 and 19 ppt). Groundwater samples showed elevated colloid bound PCDD concentrations (mean 770 ng/kg), mainly octachlorodibenzo-p-dioxin. Groundwater colloids separated by filtration did not show any TCDD. The results support that TCDD/Fs can be relocated from the top soil to the groundwater by colloidal pathway. They did not provide evidence that the dioxins bound to groundwater colloids are leftovers from the Second Indochinese War. However, this study reinforces that the colloidal transport pathway has to be included investigating the relocation of strong sorbing organic contaminants.

Environmental fate and bioavailability of Agent Orange and its associated dioxin during the Vietnam War.

BACKGROUND: In 1996, the Committee on the Assessment of Wartime Exposure to Herbicides in Vietnam of the National Academy of Sciences' Institute of Medicine (IOM) issued a report on an exposure model for use in epidemiological studies of Vietnam veterans. This exposure model would consider troop locations based on military records; aerial spray mission data; estimated ground spraying activity; estimated exposure opportunity factors; military indications for herbicide use; and considerations of the composition and environmental fate of herbicides, including changes in the TCDD content of the herbicides over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of the herbicides into the ground. When the final report of the IOM Committee was released in October 2003, several components of the exposure model envisioned by the Committee were not addressed. These components included the environmental fate of the herbicides, including changes in the TCDD content over time, the persistence of TCDD and herbicides in the environment, and the degree of likely penetration of herbicides into the ground. This paper is intended to help investigators understand better the fate and transport of herbicides and TCDD from spray missions, particularly in performing epidemiological studies. METHODS: This paper reviews the published scientific literature related to the environmental fate of Agent Orange and the contaminant, 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), and discusses how this affected the potential exposure to TCDD of ground troops in Vietnam. Specifically, the mechanisms of dissipation and degradation as they relate to environmental distribution and bioavailability are addressed. RESULTS: The evaluation of the spray systems used to disseminate herbicides in Vietnam showed that they were capable of highly precise applications both in terms of concentrations sprayed and area treated. Research on tropical forest canopies with leaf area indices (a measure of foliage density) from 2 to 5 indicated that the amount of herbicide and associated TCDD reaching the forest floor would have been between 1 and 6% of the total aerial spray. Studies of the properties of plant surface waxes of the cuticle layer suggested that Agent Orange, including the TCDD, would have dried (i.e., be absorbed into the wax layer of the plant cuticle) upon spraying within minutes and could not be physically dislodged. Studies of Agent Orange and the associated TCDD on both leaf and soil surface have demonstrated that photolysis by sunlight would have rapidly decreased the concentration of TCDD, and this process continued in shade. Studies of 'dislodgeable foliar residues' (DFR, the fraction of a substance that is available for cutaneous uptake from the plant leaves) showed that only 8% of the DFR was present 1 hr after application. This dropped to 1% of the total 24 hrs after application. Studies with human volunteers confirmed that after 2 hrs of saturated contact with bare skin, only 0.15-0.46% of 2,4,5-T, one of the phenoxy acetic acid compounds that was an active ingredient of Agent Orange, entered the body and was eliminated in the urine. CONCLUSIONS: The prospect of exposure to TCDD from Agent Orange in ground troops in Vietnam seems unlikely in light of the environmental dissipation of TCDD, little bioavailability, and the properties of the herbicides and circumstances of application that occurred. Photochemical degradation of TCDD and limited bioavailability of any residual TCDD present in soil or on vegetation suggest that dioxin concentrations in ground troops who served in Vietnam would have been small and indistinguishable from background levels even if they had been in recently treated areas. Laboratory and field data reported in the literature provide compelling evidence on the fate and dislodgeability of herbicide and TCDD in the environment. This evidence of the environmental fate and poor bioavailability of TCDD from Agent Orange is consistent with the observation of little or no exposure in the veterans who served in Vietnam. Appreciable accumulation of TCDD in veterans would have required repeated long-term direct skin contact of the type experienced by United States (US) Air Force RANCH HAND and US Army Chemical Corps personnel who handled or otherwise had direct contact with liquid herbicide, not from incidental exposure under field conditions where Agent Orange had been sprayed.

2,4,5-T and 2,4,5-TCP induce oxidative damage in human erythrocytes: the role of glutathione.

The molecular basis of the toxic properties of phenoxy herbicides in humans and animals has been insufficiently studied. In this study, damage parameters [levels of reduced glutathione (GSH) and total glutathione; activity of glutathione reductase (GR); activities of catalase (CAT) and superoxide dismutase (SOD); levels of adenine nucleotides and adenine energy charge (AEC)] were measured in human erythrocytes exposed in vitro to 2,4,5-trichlorophenoxyacetic acid (2,4,5-T) and its metabolite 2,4,5-trichlorophenol (2,4,5-TCP). Both 2,4,5-T and 2,4,5-TCP decreased the level of reduced glutathione (GSH) in erythrocytes in comparison to the control, but did not significantly change the total glutathione (2GSH + GSSG). This suggests that GSH concentration decreases concomitantly with an increase in oxidized glutathione (GSSG). 2,4,5-TCP at 100 ppm significantly decreased catalase and SOD activities. 2,4,5-T and 2,4,5-TCP did not significantly change the activity of glutathione reductase. 2,4,5-TCP decreased the level of ATP and increased the content of ADP and AMP, indicating a fall in AEC. 2,4,5-T and 2,4,5-TCP significantly changed the erythrocyte morphology. All these data are evidence of oxidative stress in erythrocytes incubated with 2,4,5-T and 2,4,5-TCP; the stress appears to be more intense in the case of 2,4,5-TCP.

Sensitive indirect photometric detection of inorganic and small organic anions by capillary electrophoresis using Orange G as a probe ion.

This study addresses the two major problems in the use of dyes as highly absorbing probes for indirect photometric detection in capillary electrophoresis (CE). First, effective electroosmotic flow (EOF) modification or suppression to allow separation and detection of a wide mobility range of analytes is not straightforward when electrolytes containing increased dye concentrations are used. The suppression of EOF to less than + 5x10(-9) m(2)V(-1)s(-1) was achieved with a combination of a poly(ethylenimine) (PEI)-coated capillary and the addition of the neutral polymer hydroxypropylmethylcellulose (HPMC) to the background electrolyte. Second, the deterioration of baselines due to adsorption of the dye probe to the capillary wall is generally a problem. In this work, baseline quality at higher probe concentrations was significantly improved by a rather unusual but highly effective combination of a simultaneous application of a slight overpressure (25 mbar) at the injection end during the separation, and the use of a relatively narrow capillary of 50 microm inner diameter. Both measures would appear to be counterproductive. Optimisation of the probe concentration with regard to signal-to-noise ratio resulted in an electrolyte of 4 mM Orange G, 0.05% HPMC buffered at pH 7.7 by the addition of 10.0 mM histidine isoelectric buffer. Very high separation efficiencies of 128 000-297 000 plates were made possible by the relatively high probe concentration. Combined with excellent detection sensitivity, even with the introduction of hydrodynamic flow and a reduced optical path length, these measures resulted in limits of detection ranging from 0.216 to 0.912 microM with a deuterium lamp light source (248 nm) and from 0.147 to 0.834 microM with a 476 nm blue light-emitting diode (LED) light source. Reproducibility over 30 consecutive runs without changing the electrolyte was excellent, with relative standard deviation (RSD) values of 0.14-0.80% for migration time, 1.27-3.36% for peak area and 0.88-5.12% for peak heights. The optimised electrolyte was used for the analysis of inorganic anions in air filter samples, providing good agreement with results obtained by ion chromatography.

Reversible surface thiol immobilization of carboxyl group containing haptens to a BIAcore biosensor chip enabling repeated usage of a single sensor surface.

We describe a reversible immobilization method for carboxyl group containing haptens that makes the repeated usage of a BIAcore biosensor chip possible. Haptens which are immobilized according to the surface thiol method can be removed completely from the sensor surface again by a reducing step. In the first part of our study, analogues of the herbicides 2,4-dichlorophenoxyacetic acid and 2,4,5-trichlorophenoxyacetic acid were immobilized in succession to a biosensor surface of a BIAcore surface plasmon resonance instrument according to the thiol coupling method. Direct kinetic analysis of these ligands to a polyclonal anti-2,4-dichlorophenoxyacetic acid antibody were performed using these biosensor surfaces. In the second part of the study, different amounts of 2,4-dichlorophenoxyacetic acid were sequentially immobilized onto the same biosensor surface in order to generate a calibration plot for 2,4-dichlorophenoxyacetic acid. Using this plot, the quantitative detection of the herbicide down to a concentration of 0.1 microg/mL, the maximum admissible concentration of pesticides in drinking water, is possible.