Mercury mobility and effects in the salt-marsh plant Halimione portulacoides: Uptake, transport, and toxicity and tolerance mechanisms.

The plant Halimione portulacoides, an abundant species widely distributed in temperate salt-marshes, has been previously assessed as bioindicator and biomonitor of mercury contamination in these ecosystems. The present study aims to assess uptake and distribution of total mercury (THg) and methylmercury (MMHg) within H. portulacoides, potential mercury release by volatilization through leaves, and toxicity and tolerance mechanisms by investigating plant photochemical responses. Stem cuttings of H. portulacoides were collected from a salt-marsh within the Tagus estuary natural protected area, and grown under hydroponic conditions. After root development, plants were exposed to 199HgCl2 and CH3201HgCl, and sampled at specific times (0, 1, 2, 4, 24, 72, 120, 168 (7 days) and 432 h (18 days)). After exposure, roots, stems and leaves were analysed for total 199Hg (T199Hg) and MM201Hg content. Photobiology parameters, namely efficiency and photoprotection capacity, were measured in leaves. Both THg and MMHg were incorporated into the plant root system, stems and leaves, with roots showing much higher levels of both isotope enriched spikes than the other plant tissues. Presence of both mercury isotopes in the stems and leaves and high significant correlations found between roots and stems, and stems and leaves, for both THg and MMHg concentrations, indicate Hg translocation between the roots and above-ground organs. Long-term uptake in stems and leaves, leading to higher Hg content, was more influenced by temperature and radiation than short-term uptake. However, the relatively low levels of both THg and MMHg in the aerial parts of the plant, which were influenced by temperature and radiation, support the possibility of mercury release by stems and leaves, probably via stomata aperture, as a way to eliminate toxic mercury. Regarding photochemical responses, few differences between control and exposed plants were observed, indicating high tolerance of this salt marsh plant to THg and MMHg.

Direct Photolysis of Sulfamethoxazole Using Various Irradiation Sources and Wavelength Ranges-Insights from Degradation Product Analysis and Compound-Specific Stable Isotope Analysis.

The environmental micropollutant sulfamethoxazole (SMX) is susceptible to phototransformation by sunlight and UV-C light which is used for water disinfection. Depending on the environmental pH conditions SMX may be present as neutral or anionic species. This study systematically investigates the phototransformation of these two relevant SMX species using four different irradiation scenarios, i.e., a low, medium, and high pressure Hg lamp and simulated sunlight. The observed phototransformation kinetics are complemented by data from compound-specific stable isotope and transformation product analysis using isotope-ratio and high-resolution mass spectrometry (HRMS). Observed phototransformation kinetics were faster for the neutral than for the anionic SMX species (from 3.4 (LP lamp) up to 6.6 (HP lamp) times). Furthermore, four phototransformation products (with m/z 189, 202, 242, and 260) were detected by HRMS that have not yet been described for direct photolysis of SMX. Isotopic fractionation occurred only if UV-B and UV-A wavelengths prevailed in the emitted irradiation and was most pronounced for the neutral species with simulated sunlight (εC = -4.8 ± 0.1 ‰). Phototransformation of SMX with UV-C light did not cause significant isotopic fractionation. Consequently, it was possible to differentiate sunlight and UV-C light induced phototransformation of SMX. Thus, CSIA might be implemented to trace back wastewater point sources or to assess natural attenuation of SMX by sunlight photolysis. In contrast to the wavelength range, pH-dependent speciation of SMX hardly impacted isotopic fractionation.

Degradation of sulfamethoxazole using ozone and chlorine dioxide - Compound-specific stable isotope analysis, transformation product analysis and mechanistic aspects.

The sulfonamide antibiotic sulfamethoxazole (SMX) is a widely detected micropollutant in surface and groundwaters. Oxidative treatment with e.g. ozone or chlorine dioxide is regularly applied for disinfection purposes at the same time exhibiting a high potential for removal of micropollutants. Especially for nitrogen containing compounds such as SMX, the related reaction mechanisms are largely unknown. In this study, we systematically investigated reaction stoichiometry, product formation and reaction mechanisms in reactions of SMX with ozone and chlorine dioxide. To this end, the neutral and anionic SMX species, which may occur at typical pH-values of water treatment were studied. Two moles of chlorine dioxide and approximately three moles of ozone were consumed per mole SMX degraded. Oxidation of SMX with ozone and chlorine dioxide leads in both cases to six major transformation products (TPs) as revealed by high-resolution mass spectrometry (HRMS). Tentatively formulated TP structures from other studies could partly be confirmed by compound-specific stable isotope analysis (CSIA). However, for one TP, a hydroxylated SMX, it was not possible by HRMS alone to identify whether hydroxylation occurred at the aromatic ring, as suggested in literature before, or at the anilinic nitrogen. By means of CSIA and an analytical standard it was possible to identify sulfamethoxazole hydroxylamine unequivocally as one of the TPs of the reaction of SMX with ozone as well as with chlorine dioxide. H-abstraction and electron transfer at the anilinic nitrogen are suggested as likely initial reactions of ozone and chlorine dioxide, respectively, leading to its formation. Oxidation of anionic SMX with ozone did not show any significant isotopic fractionation whereas the other reactions studied resulted in a significant carbon isotope fractionation.

Excess Electron Transfer through DNA Duplexes Comprising a Metal-Mediated Base Pair.

Excess electron transfer through one set of DNA duplexes comprising either one or two metal-mediated thymine-HgII -thymine base pairs was studied. Towards this end, the metal-mediated base pair(s) were introduced between an artificial nucleoside bearing a N,N,N',N'-tetramethyl-1,5-diaminonaphthalene derivative (dN, acting as a photoinducible electron donor) and 5-bromo-2'-deoxyuridine (dB, acting as an electron acceptor). Upon one-electron reduction, dB loses a bromide ion. The amount of unreacted dB remaining after irradiation-determined by LC/ICP-MS-was used to evaluate the charge-transfer efficiency across the metal-mediated base pair(s). Reference measurements with canonical adenine:thymine base pairs prove the applicability of this approach for the detection of charge transfer in DNA. The data indicate that, for the set of DNA duplexes under investigation, excess electron transfer across a thymine-HgII -thymine base pair proceeds with low efficiency, comparable to the transfer across a thymine:thymine mispair. Two contiguous thymine-HgII -thymine base pairs effectively shut down excess electron transfer.

Evaluation of mercury methylation and methylmercury demethylation rates in vegetated and non-vegetated saltmarsh sediments from two Portuguese estuaries.

Neurotoxic methylmercury (MMHg) is formed from inorganic divalent mercury (Hg2+). However, it is poorly understood to what extent different mercury (Hg) pools contribute to existent MMHg levels. In this study, ambient concentrations of total Hg (THg) and MMHg as well as rates of methylation and demethylation were measured simultaneously in sediments with and without salt-marsh plant vegetation, which were collected in Guadiana and Tagus estuaries, Portugal. Concurrent processes of Hg methylation and MMHg demethylation were directly monitored and compared by spiking sediments cores with stable isotope tracers of 199Hg2+ and CH3201Hg+ followed by gas chromatographic separation and isotope-specific detection using inductively coupled plasma mass spectrometry. Compared to the Guadiana estuary, where concentrations were comparatively low, THg and MMHg levels varied between vegetated and non-vegetated sediments collected at the Rosário site (ROS) of the Tagus estuary. Methylation (KM) and demethylation rates (KD) were also different between estuaries being dependent on the presence of vegetation. In addition, the type of macrophyte species influenced KM and KD values. In fact, the highest KM value was found in Sarcocornia fruticosa vegetated sediments at the Castro Marim site in Guadiana (CM, 0.160 day-1) and the lowest KM was observed in non-vegetated sediments at the Alcochete site in Tagus (ALC, 0.009 day-1). KD varied by a factor of three among sites with highest rates of demethylation observed in non-vegetated sediments in Guadiana (12 ± 1.3 day-1, corresponding to a half-life of 1.4 ± 0.2 h). This study clearly shows that the presence of vegetation in sediments favors the formation of MMHg. Moreover, this effect might be site specific and further studies are needed to confirm the findings reported here.