Abscisic acid-dependent PMT1 expression regulates salt tolerance by alleviating abscisic acid-mediated reactive oxygen species production in Arabidopsis.

Phosphocholine (PCho) is an intermediate metabolite of nonplastid plant membranes that is essential for salt tolerance. However, how PCho metabolism modulates response to salt stress remains unknown. Here, we characterize the role of phosphoethanolamine N-methyltransferase 1 (PMT1) in salt stress tolerance in Arabidopsis thaliana using a T-DNA insertional mutant, gene-editing alleles, and complemented lines. The pmt1 mutants showed a severe inhibition of root elongation when exposed to salt stress, but exogenous ChoCl or lecithin rescued this defect. pmt1 also displayed altered glycerolipid metabolism under salt stress, suggesting that glycerolipids contribute to salt tolerance. Moreover, pmt1 mutants exhibited altered reactive oxygen species (ROS) accumulation and distribution, reduced cell division activity, and disturbed auxin distribution in the primary root compared with wild-type seedlings. We show that PMT1 expression is induced by salt stress and relies on the abscisic acid (ABA) signaling pathway, as this induction was abolished in the aba2-1 and pyl112458 mutants. However, ABA aggravated the salt sensitivity of the pmt1 mutants by perturbing ROS distribution in the root tip. Taken together, we propose that PMT1 is an important phosphoethanolamine N-methyltransferase participating in root development of primary root elongation under salt stress conditions by balancing ROS production and distribution through ABA signaling.

Monitoring of arsenic, mercury and organic pesticides in particulate matter, ambient air and settled dust in natural history collections taking the example of the Museum für Naturkunde, Berlin.

Chemical compounds such as arsenic, mercury and organochlorine pesticides have been extensively used as preventive and curative conservation treatments for cultural and biological collections to protect them from pest and mould infestations. Most of the aforementioned compounds have been classified as carcinogenic, mutagenic and teratogenic and represent a health risk for staff exposed to contaminated objects. A total of 30 compounds were analysed in settled dust, particulate matter and surrounding air collected at several locations in the natural history collections and adjacent rooms of the Museum für Naturkunde, Berlin (MfN, Natural History Museum, Berlin, Germany). Gas chromatography and mass spectrometry techniques were used to quantify dichlorodiphenyltrichloroethane (2,4'-DDT; 4,4'-DDT) and their metabolites (2,4'-DDE; 4,4'-DDE; 2,4'-DDD; 4,4'-DDD), hexachlorobenzene (HCB), 3 isomers of hexachlorocyclohexanes (α-HCH, ß-HCH, γ-HCH), the degradation product of γ-HCH with similar toxicological profile, gamma-pentachlorocyclohexene (γ-PCH) and pentachlorophenol (PCP). Atomic absorption spectrometry was used to analyse arsenic and mercury. In order to assess the pathways of contamination with biocides in dust, formations of particulate matter during individual daily work activities, particle number concentrations (PNCs) were measured. Heavy element concentrations found at the MfN were higher than the organochlorine compounds. The maximum concentration of arsenic and mercury in dust was 3507 mg/kg and 32 mg/kg, respectively, and in air, 48 ng/m3 and 1.6 ng/m3, respectively. The maximum concentration of the sum of DDTs in dust was 2 mg/kg (not detected in air); for PCP, the maximum levels in dust and air were 0.65 mg/kg and 10 ng/m3, respectively; for γ-HCH, 130 mg/kg and 320 ng/m3, respectively; and finally, for γ-PCH, 2.1 mg/kg and 230 ng/m3, respectively. Twelve PNC measurements were obtained from seven different collection rooms and the diaries of the participants' activities. PNCs were highly variable between work activities. Higher personal PNCs were associated with activities like opening storage boxes with prepared animals, reading old books or handling objects. This study has shown that taxidermic objects in museum collection may be a cause for arsenic exposure during handling of objects.

γ-BHC: Its history and mystery--why is only γ-BHC insecticidal?

Among BHC isomers (benzene hexachloride, C6H6Cl6, theoretically eight ones), seven isomers (α,ß,γ,δ,ε,η,ι) including one racemate (α) were isolated and their configurations were elucidated. Among the seven isomers, only γ-BHC has a potent insecticidal activity. γ-BHC poisoning symptoms accompanied by the violent tremor of the body, particularly in the legs and abnormal fluttering were consistently correlated with central nervous system effects, and the action was shown on the ganglia rather than on the isolated nerve cord. The excitatory effects of γ-BHC poisoning on spontaneous activity and synaptic function in the sixth abdominal ganglion of the American cockroach result from the presynaptic action that causes an excessive release of acetylcholine. F. Matsumura found the phenomena of cross resistance between γ-BHC, cyclodiene insecticides and GABA (γ-aminobutyric acid) antagonist, picrotoxinin, and concluded that the primary target of γ-BHC is the picrotoxinin receptor in the GABA receptor Cl- ion channel complex (GABA-gated chloride channel) and its antagonistic action on GABA receptor results in an excessive release of Ach. In order to study the structure-activity relationship, a number of γ-BHC analogs, in which one or two chlorine atoms on dl or meso position(s) of the γ-BHC molecule were replaced by various substituents such as hydrogen, halogens other than chlorine and alkoxy groups, etc. were synthesized. In the case of dl type-analogs, there is an optimum volume for dl-substituents, which corresponds to Cl. The question why γ-BHC is insecticidal and other BHC isomers are not remains unsolved.

A Five-Week Periodized Carbohydrate Diet Does Not Improve Maximal Lactate Steady-State Exercise Capacity and Substrate Oxidation in Well-Trained Cyclists compared to a High-Carbohydrate Diet.

There is a growing interest in studies involving carbohydrate (CHO) manipulation and subsequent adaptations to endurance training. This study aimed to analyze whether a periodized carbohydrate feeding strategy based on a daily training session has any advantages compared to a high-carbohydrate diet in well-trained cyclists. Seventeen trained cyclists (VO2peak = 70.8 ± 6.5 mL·kg-1·min-1) were divided into two groups, a periodized (PCHO) group and a high-carbohydrate (HCHO) group. Both groups performed the same training sessions for five weeks. In the PCHO group, 13 training sessions were performed with low carbohydrate availability. In the HCHO group, all sessions were completed following previous carbohydrate intake to ensure high pre-exercise glycogen levels. In both groups, there was an increase in the maximal lactate steady state (MLSS) (PCHO: 244.1 ± 29.9 W to 253.2 ± 28.4 W; p = 0.008; HCHO: 235.8 ± 21.4 W to 246.9 ± 16.7 W; p = 0.012) but not in the time to exhaustion at MLSS intensity. Both groups increased the percentage of muscle mass (PCHO: p = 0.021; HCHO: p = 0.042) and decreased the percent body fat (PCHO: p = 0.021; HCHO: p = 0.012). We found no differences in carbohydrate or lipid oxidation, heart rate, and post-exercise lactate concentration. Periodizing the CHO intake in well-trained cyclists during a 5-week intervention did not elicit superior results to an energy intake-matched high-carbohydrate diet in any of the measured outcomes.

Enantioselective dehydrochlorination of δ-Hexachlorocyclohexane and δ-Pentachlorocyclohexene by LinA1 and LinA2 from Sphingobium indicum B90A.

δ-Hexachlorocyclohexane (δ-HCH), one of the prevalent isomers of technical HCH, was enantioselectively dehydrochlorinated by the dehydrochlorinases LinA1 and LinA2 from Sphingobium indicum B90A to the very same δ-pentachlorocyclohexene enantiomer. Racemic δ-pentachlorocyclohexene, however, was transformed with opposite enantioselectivities by the two enzymes. A transformation pathway based on an anti-1,2-elimination, followed by a syn-1,4-elimination and a subsequent syn-1,2-elimination is postulated.

Polyaniline-based highly sensitive microbial biosensor for selective detection of lindane.

A highly sensitive, selective, and rapid, whole-cell-based electrochemical biosensor was developed for detection of the persistent organochlorine pesticide γ-hexachlorocyclohexane (γ-HCH), commonly known as lindane. The gene linA2 encoding the enzyme γ-hexachlorocyclohexane (HCH) dehydrochlorinase (LinA2), involved in the initial steps of lindane (γ-HCH) biotransformation, was cloned and overexpressed in Escherichia coli . The lindane-biodegrading E. coli cells were immobilized on polyaniline film. The rapid and selective degradation of lindane and concomitant generation of hydrochloric acid by the recombinant E. coli cells in the microenvironment of polyaniline led to a change in its conductivity, which was monitored by pulsed amperometry. The biosensor could detect lindane in the part-per-trillion concentration range with a linear response from 2 to 45 ppt. The sensor was found to be selective to all the isomers of hexachlorocyclohexane (HCH) and to pentachlorocyclohexane (PCCH) but did not respond to other aliphatic and aromatic chlorides or to the end product of lindane degradation, i.e., trichlorobenzene (TCB). The sensor also did not respond to other commonly used organochlorine pesticides like DDT and DDE. On the basis of experimental results, a rationale has been proposed for the excellent sensitivity of polyaniline as a pH sensor for detection of H(+) ions released in its microenvironment.

Partitioning of chlorinated organic compounds from dense non-aqueous phase liquids and contaminated soils from lindane production wastes to the aqueous phase.

Hexachlorocyclohexane (HCH) and mainly the γ-HCH isomer, namely lindane, were extensively produced and used as pesticides. Huge amounts of wastes, solids and liquids, were disposed of in the surroundings of the production sites. The liquid residuum was a complex mixture of chlorinated organic compounds, COCs, from chlorobenzene to heptachlorocyclohexane. This Dense Non-Aqueous Phase Liquid, DNAPL, migrated by density through the subsurface to greater depths, being trapped or adsorbed into the soil in this movement posing a significant risk to the groundwater. Knowledge of the partitioning in water of COCs in DNAPL is a key issue to determine its fate in the environment. However, there are no data in literature for the partitioning and/or solubility of many of the COCs in this DNAPL, such as pentachlorocyclohexene, hexachlorocyclohexene and heptachlorocyclohexane despite them constitute about 13-30% of the mole fraction of the DNAPLs. In this work, the partitioning to water of COCs in free and those adsorbed onto soil has been studied. In addition, measured and predicted aqueous concentrations of each COC in the DNAPL mixture have been compared. To do this, the solubility of a compound that is a solid crystal when pure at P = 298 K and P = 1 atm has been evaluated considering the approach of sub-cooled liquid state of solid organochlorines. Samples were obtained at Sabiñanigo landfills and soils used had several grain sizes. Transformation in alkaline media of COCs had a positive environmental impact.

Hexachlorocyclohexane derivatives in industrial waste and samples from a contaminated riverine system.

Side and initial degradation products of the persistent organic pollutant hexachlorocyclohexane (HCH) were largely neglected in environmental analysis so far. However, these compounds can be indicative for biodegradation or emission sources. Thus, several samples from a contaminated riverine system in vicinity to a former HCH production site in Central Germany were analyzed. This area adjacent to the industrial megasite Bitterfeld-Wolfen is known for elevated concentrations of various organic industrial pollutants as legacy of decades of industrial activity and subsequent deposition of chemical waste and emission of waste effluents. In environmental compartments of this riverine system, several isomers of HCH related compounds were detected comprising the two lower chlorinated species tetrachlorocyclohexene (TeCCH) and pentachlorocyclohexene (PeCCH) and the higher chlorinated species heptachlorocyclohexane (HpCCH). Except for the uppermost soil of an analyzed riparian wetland, concentrations of these compounds were low. Detected isomers in sediment, water, and soil samples correlated and dominant isomers of PeCCH and HpCCH were observed in the alluvial deposits. Comparisons with industrial HCH waste revealed isomeric patterns similar to patterns found in soil samples. Therefore, the application of HpCCH as an indicator of industrial HCH pollution is suggested.

Organochlorine pesticides accumulation and degradation products in vegetation samples of a contaminated area in Galicia (NW Spain).

The content of 21 organochlorine pesticides were studied in vegetation samples of a highly contaminated area by isomers of hexachlorocyclohexane (HCH) located close to a former industrial area in Galicia (NW Spain). Five species of plants were collected at different points of the contaminated area and the different parts of the plants were separated in order to study differences in accumulation capabilities. Samples were extracted employing microwave energy followed by a clean-up step using solid phase extraction and finally determined by GC-ECD. The results obtained show that the most abundant pesticides are HCHs isomers, being the main isomers beta-HCH and alpha-HCH in all samples whereas delta-HCH and gamma-HCH were at lower levels. Some other pesticides such as p,p'-DDT, p,p'-DDD and p,p'-DDE were also present in much lower amount in some of the samples. Several degradation products of HCH were also identified in some samples by GC-MS.

Organochlorine residues in odontocete species from the southeast coast of India.

Blubber from bottle-nose dolphins, spinner dolphins, humpback dolphin (Tursiops truncatus, Stenella longirostris and Sousa chinensis) were collected from the Bay of Bengal (southeast coast of India) and analyzed for the organochlorine pesticides hexachlorocyclohexane (HCHs), p,p'-dichlorodiphenyl trichloroethane (DDTs), and polychlorinated biphenyls (PCBs). All nine specimens analyzed contained considerable levels of all the three chemical classes where DDT was in the range of 3330-23330 ng/g; HCHs in the range of 95-765 ng/g; and PCBs in the range of 210-1220 ng/g (wet weight basis). The reasons for this and the variations in the isomer pattern of HCHs and DDT and its metabolites in marine mammal tissues are discussed.

Air-water gas exchange of chlorinated pesticides in four lakes spanning a 1,205 meter elevation range in the Canadian Rocky Mountains.

Concentrations of selected persistent organic pollutants (POPs) in air and water were measured from four lakes that transect the Canadian Rocky Mountains. These data were used in combination with wind velocity and temperature-adjusted Henry's law constants to estimate the direction and magnitude of chemical exchange across the air-water interface of these lakes. Bow Lake (1,975 m above sea level [masl]) was studied during the summers of 1998 through 2000; Donald (770 masl) was studied during the summer of 1999; Dixon Dam Lake (946 masl) and Kananaskis Lake (1,667 masl) were studied during the summer of 2000. Hexachlorobenzene (HCB) and dieldrin volatilized from Bow Lake in spring and summer of 1998 to 2000 at a rate of 0.92 +/-1.1 and 0.55+/-0.37 ng m(-2) d(-1), respectively. The alpha-endosulfan deposited to Bow Lake at a rate of 3.4+/-2.2 ng m(-2) d(-1). Direction of gas exchange for gamma-hexachlorocyclohexane (gamma-HCH) changed from net deposition in 1998 to net volatilization in 1999, partly because of a surge in y-HCH concentrations in the water at Bow Lake in 1999. Average gamma-HCH concentrations in air declined steadily over the three-year period, from 0.021 ng m(-3) in 1998, to 0.0023 ng m(-3) in 2000, and to volatilization in 1999 and 2000. Neither the concentrations of organochlorine compounds (OCs) in air and water, nor the direction and rate of air-water gas exchange correlate with temperature or elevation. In general, losses of pesticides by outflow were greater than the amount exchanged across the air-water interface in these lakes.

Brain metabolites of lindane and related isomers: identification by negative ion mass spectrometry.

The application of a new method of gas chromatography-mass spectrometry (GC-MS) to the study of some aspects of the metabolism of hexachlorocyclohexanes is presented. Instead of the classical mode of ionization (Electron Impact, EI), this method uses chemical ionization, recording only the negative ions produced. This enables a tremendous enhancement of the signal when chlorinated compounds elute from the chromatographic column. The mass spectra obtained consist generally in the ions corresponding to the molecular weight of the compound analyzed. The sensitivity of the method is higher than any other GC method described: the limit of detection of several organochlorine compounds can be as low as 60 femtograms. Using this method we have been able to identify several Lindane metabolites (tetra-, penta- and hexachlorocyclohexenes, tetra- and pentachlorobenzene) in rat brain homogenates without any purification step. Using this method, a quantitative study of the main metabolites found in brain after treatment with 4 different HCH isomers has been performed. This study reveals that the HCH isomers are cleared from the brain via different metabolic pathways, with a rate of production of metabolites which is inversely correlated to their half lives in brain.

Effect of 11 beta-substituents on the regioselective chlorination of estrogens with 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone.

The reaction of 11 beta-substituted estrogens with 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone affords exclusively ortho-substituted monochlorinated products including a major 4-chloro and a minor 2-chloro derivative. In the absence of an 11 beta-substituent, regioselectivity is lost, resulting in a mixture of 10 beta- and ortho-chlorinated products.

Kinetics of bioaccumulation and clearance of isomeric hexachlorocyclohexanes.

Bioaccumulation experiments were performed on the hexachlorocyclohexane isomers alpha-HCH, beta-HCH, gamma-HCH and delta-HCH, testing them simultaneously. Bioaccumulation factors (BCFs) were calculated from the uptake rate constant (k1) and the clearance rate constant (k2) as: BCF = k1/k2. The BCFs of alpha-HCH (1100 +/- 175) and gamma-HCH (920 +/- 131) were similar. The BCFs of beta-HCH (1520 +/- 276) and delta-HCH (1640 +/- 269), also similar, were significantly higher than those of the alpha- and gamma-isomers.

Air-water gas exchange and evidence for metabolism of hexachlorocyclohexanes in Resolute Bay, N.W.T.

Paired air and water samples were collected at Resolute Bay (74 degrees N, 95 degrees W) in summer 1992 to estimate the direction of gas exchange of hexachlorocyclohexanes (HCHs) and investigate possible loss processes in the water column. Average concentrations of alpha-HCH and gamma-HCH in ocean surface water were 4.7 +/- 0.9 and 0.44 +/- 0.11 ng/l, respectively. These alpha- and gamma-HCH levels are approximately 66-104% and 54-72% of values reported for the central Arctic Ocean at the Canadian Ice Island in 1986. Mean atmospheric concentrations of alpha-HCH and gamma-HCH (114 +/- 16 and 9.8 +/- 1.3 pg/m3) were 2-3 times lower than summer Arctic levels in the 1980s. The ocean surface water (-1.4 degrees C) was approximately within Henry's Law equilibrium with respect to atmospheric gamma-HCH levels. Water/air fugacity ratios were 1.03 for gamma-HCH and 1.57 for alpha-HCH, indicating a slight potential for volatilization of alpha-HCH. The two alpha-HCH enantiomers in air and water were separated by chromatography on a gamma-cyclodextrin capillary column. The enantiomeric ratio (ER = ratio of (+)alpha-HCH/(-)alpha-HCH) in air was 1.00 +/- 0.04. This agrees excellently with ER = 1.00 +/- 0.01 found for a racemic alpha-HCH standard. The (+) enantiomer was depleted in seawater, resulting in ER = 0.93 +/- 0.06 in Resolute Bay. ERs of samples from Amituk Lake on Cornwallis Island ranged from 0.65 to 0.99, depending on location, date and relative contributions of fresh snowmelt and older lake water. These results suggest that microbial degradation of HCHs is taking place in Arctic lakes and near-shore marine waters.

The release of lindane from contaminated building materials.

The release of the organochlorine pesticide lindane (γ-hexachlorocyclohexane) from several types of contaminated building materials was studied to assess inhalation hazard and decontamination requirements in response to accidental and/or intentional spills. The materials included glass, polypropylene carpet, latex-painted drywall, ceramic tiles, vinyl floor tiles, and gypsum ceiling tiles. For each surface concentration, an equilibrium concentration was determined in the vapour phase of the surrounding air. Vapor concentrations depended upon initial surface concentration, temperature, and type of building material. A time-weighted average (TWA) concentration in the air was used to quantify the health risk associated with the inhalation of lindane vapors. Transformation products of lindane, namely α-hexachlorocyclohexane and pentachlorocyclohexene, were detected in the vapour phase at both temperatures and for all of the test materials. Their formation was greater on glass and ceramic tiles, compared to other building materials. An empiric Sips isotherm model was employed to approximate experimental results and to estimate the release of lindane and its transformation products. This helped determine the extent of decontamination required to reduce the surface concentrations of lindane to the levels corresponding to vapor concentrations below TWA.

Hexachlorocyclohexane (HCH) as new Stockholm Convention POPs--a global perspective on the management of Lindane and its waste isomers.

PURPOSE: Hexachlorocyclohexane (HCH) isomers (α-, ß- and γ- (Lindane)) were recently included as new persistent organic pollutants (POPs) in the Stockholm Convention, and therefore, the legacy of HCH and Lindane production became a contemporary topic of global relevance. This article wants to briefly summarise the outcomes of the Stockholm Convention process and make an estimation of the amount of HCH waste generated and dumped in the former Lindane/HCH-producing countries. RESULTS: In a preliminary assessment, the countries and the respective amount of HCH residues stored and deposited from Lindane production are estimated. Between 4 and 7 million tones of wastes of toxic, persistent and bioaccumulative residues (largely consisting of alpha- (approx. 80%) and beta-HCH) are estimated to have been produced and discarded around the globe during 60 years of Lindane production. For approximately 1.9 million tones, information is available regarding deposition. Countries are: Austria, Brazil, China, Czech Republic, France, Germany, Hungary, India, Italy, Japan, Macedonia, Nigeria, Poland, Romania, Slovakia, South Africa, Spain, Switzerland, Turkey, The Netherlands, UK, USA, and former USSR. The paper highlights the environmental relevance of deposited HCH wastes and the related POPs' contaminated sites and provides suggestions for further steps to address the challenge of the legacy of HCH/Lindane production. CONCLUSION: It can be expected that most locations where HCH waste was discarded/stockpiled are not secured and that critical environmental impacts are resulting from leaching and volatilization. As parties to the Stockholm Convention are legally required to take action to stop further POPs pollution, identification and evaluation of such sites are necessary.

Hexachlorocyclohexanes in the Canadian archipelago. 1. Spatial distribution and pathways of alpha-, beta- and gamma-HCHS in surface water.

Hexachlorocyclohexanes (HCHs) in the surface water of the Canadian Archipelago and south Beaufort Sea were measured in summer, 1999. Overall concentrations of HCH isomers were in order of abundance: alpha-HCH (3.5 +/- 1.2 ng L(-1)) > gamma-HCH (0.31 +/- 0.07 ng L(-1)) > beta-HCH (0.10 +/- 0.03 ng L(-1)). Concentrations and ratios of alpha-HCH/gamma-HCH decreased significantly (p < 0.001 to 0.003) from west to east, but there was no significant variation in alpha-HCH/ beta-HCH. The (+) enantiomer of alpha-HCH was preferentially degraded, with enantiomer fractions (EFs) ranging from 0.432-0.463 and increasing significantly (p < 0.001) from west to east. Concentrations also varied latitudinally for alpha-HCH and gamma-HCH (p < 0.002) but not for beta-HCH. Principal component analysis with variables alpha-HCH and gamma-HCH concentrations, EF, latitude, and longitude accounted for 71% (PC 1) and 16% (PC 2) of the variance. Mixing in the eastern Archipelago was modeled by assuming three end members with characteristic concentrations of alpha-HCH and gamma-HCH. The model accounted for the observed concentrations and higher EFs of alpha-HCH at the eastern stations.

Enhanced biodegradation of beta- and delta-hexachlorocyclohexane in the presence of alpha- and gamma-isomers in contaminated soils.

The chlorinated insecticide hexachlorocyclohexane (HCH) has been used extensively in the past, and contaminated sites are present throughout the world. Toward their bioremediation, we isolated a bacterium Pseudomonas aeruginosa ITRC-5 that mediates the degradation of all the four major isomers of HCH under aerobic conditions, both in liquid-culture and contaminated soils. In liquid-culture, the degradation of alpha- and gamma-HCH is rapid and is accompanied with the release of 5.6 micromole chloride ions and 4.1 micromole CO2 micromole(-1) HCH-isomer. The degradation of beta- and delta-isomers is slow, accompanied with the release of 0.9 micromole chloride ions micromole(-1) HCH-isomer, and results in a transient metabolite 2,3,4,5,6-pentachlorocyclohexan-1-ol. The strain ITRC-5 also mediates the degradation of alpha-, beta-, gamma-, and delta-isomers in contaminated soils, where degradation of otherwise persistent beta- and delta-HCH is enhanced severalfold in the presence of alpha- or gamma-HCH. The degradation of soil-applied beta- and delta-HCH under aerobic conditions has not been reported earlier. The isolate ITRC-5 therefore demonstrates potential for the bioremediation of HCH-wastes and contaminated soils.