Humic Substance Photosensitized Degradation of Phthalate Esters Characterized by 2H and 13C Isotope Fractionation

The photosensitized transformation of organic chemicals is an important degradation mechanism in natural surface waters, aerosols, and water films on surfaces. Dissolved organic matter including humic-like substances (HS), acting as photosensitizers that participate in electron transfer reactions, can generate a variety of reactive species, such as OH radicals and excited triplet-state HS (3HS*), which promote the degradation of organic compounds. We use phthalate esters, which are important contaminants found in wastewaters, landfills, soils, rivers, lakes, groundwaters, and mine tailings. We use phthalate esters as probes to study the reactivity of HS irradiated with artificial sunlight. Phthalate esters with different side-chain lengths were used as probes for elucidation of reaction mechanisms using 2H and 13C isotope fractionation. Reference experiments with the artificial photosensitizers 4,5,6,7-tetrachloro-2′,4′,5′,7′-tetraiodofluorescein (Rose Bengal), 3-methoxy-acetophenone (3-MAP), and 4-methoxybenzaldehyde (4-MBA) yielded characteristic fractionation factors (−4 ± 1, −4 ± 2, and −4 ± 1‰ for 2H; 0.7 ± 0.2, 1.0 ± 0.4, and 0.8 ± 0.2‰ for 13C), allowing interpretation of reaction mechanisms of humic substances with phthalate esters. The correlation of 2H and 13C fractions can be used diagnostically to determine photosensitized reactions in the environment and to differentiate among biodegradation, hydrolysis, and photosensitized HS reaction

Deuterium Isotope Probing: a potential game-changer in assessing chemical persistency in soil

Chemical persistency studies are crucial for the regulatory risk assessment of chemicals. One of their major challenges is the formation of so-called non-extractable residues (NERs) in soil as current analytics cannot easily differentiate hazardous xenobiotic NERs from harmless biogenic NERs (bioNERs). Widely-used radiocarbon (14C) tracing allows a rapid quantitation of total NERs whereas stable isotope labeling (13C or 15N) can track bioNERs but is not economically efficient. This study investigated the potential of deuterium isotope probing (DIP) as a new method to simplify the risk assessment associated with xenobiotic NER (xenoNER) formation. Deuterium (D) and 13C tracers were used to study the simulated degradation of three model compounds in soil, the results of which showed negligible incorporation of D into bioNERs as compared to 13C. This indicates the high potential of DIP for a rapid estimation of the hazardous xenoNERs, which could simplify chemical persistency studies in soil

Deformation Mechanisms in Ni-Based Superalloys at Room and Elevated Temperatures Studied by In Situ Neutron Diffraction and Electron Microscopy

Polycrystalline Ni-based superalloys are one of the most frequently used materials for high temperature load-bearing applications due to their superior mechanical strength and chemical resistance. In this paper, we presented an in situ diffraction study on the tensile deformation behavior of the polycrystalline Ni-based superalloy VDM® Alloy 780 at temperatures up to 500 °C performed at the STRESS-SPEC neutron diffractometer at the Heinz Maier-Leibnitz Zentrum. A detailed microstructural investigation was carried out by electron microscopy before and after testing. The results of these studies allowed us to determine the deformation mechanism in the differently orientated grains. It is shown that the deformation behavior, which is mainly dislocation motion and shearing of the γ′-precipitates, does not change at this temperature range. The deformation is strongly anisotropic and depends on the grain orientation. The macroscopic hardening can mainly be attributed to plastic deformation in grains, where the (200) lattice planes were orientated perpendicular to the loading direction. Accordingly, a remaining lattice strain and high dislocation density were detected predominantly in these grains

Multi-element compound specific stable isotope analysis of chlorinated aliphatic contaminants derived from chlorinated pitches

International audienceTetrachloroethene and trichloroethene are typical by-products of the industrial production of chloromethanes. These by-products are known as "chlorinated pitches" and were often dumped in un-contained waste disposal sites causing groundwater contaminations. Previous research showed that a strongly depleted stable carbon isotope signature characterizes chlorinated compounds associated with chlorinated pitches whereas manufactured commercial compounds have more enriched carbon isotope ratios. The findings were restricted to a single case study and one element (i.e. carbon). This paper presents a multi-element Compound-Specific Stable Isotope Analysis (CSIA, including carbon, chlorine and hydrogen) of chlorinated aliphatic contaminants originated from chlorinated pitches at two sites with different hydrogeology and different producers of chloromethanes. The results show strongly depleted carbon signatures at both sites whereas the chlorine and the hydrogen signatures are comparable to those presented in the literature for manufactured commercial compounds. Multi-element CSIA allowed the identification of sources and site-specific processes affecting chloroethene transformation in groundwater as a result of emergency remediation measures. CSIA turned out to be an effective forensic tool to address the liability for the contamination, leading to a conviction for the crimes of unintentional aggravated public water supply poisoning and environmental disaster

Enrichment of ANME-2 dominated anaerobic methanotrophy from cold seep sediment in an external ultrafiltration membrane bioreactor

Anaerobic oxidation of methane (AOM) coupled to sulfate reduction is a microbially mediated unique natural phenomenon with an ecological relevance in the global carbon balance and potential application in biotechnology. This study aimed to enrich an AOM performing microbial community with the main focus on anaerobic methanotrophic archaea (ANME) present in sediments from the Ginsburg mud volcano (Gulf of Cadiz), a known site for AOM, in a membrane bioreactor (MBR) for 726 days at 22 (± 3)°C and at ambient pressure. The MBR was equipped with a cylindrical external ultrafiltration membrane, fed a defined medium containing artificial seawater and operated at a cross flow velocity of 0.02 m/min. Sulfide production with simultaneous sulfate reduction was in equimolar ratio between days 480 and 585 of MBR operation, whereas methane consumption was in oscillating trend. At the end of the MBR operation (day 726), the enriched biomass was incubated with 13C labeled methane, 13C labeled inorganic carbon was produced and the AOM rate based on 13C-inorganic carbon was 1.2 μmol/(gdw d). Microbial analysis of the enriched biomass at 400 and 726 days of MBR operation showed that ANME-2 and Desulfosarcina type sulfate reducing bacteria were enriched in the MBR, which formed closely associated aggregates. The major relevance of this study is the enrichment of an AOM consortium in a MBR system which can assist to explore the ecophysiology of ANME and provides an opportunity to explore the potential application of AOM

Investigation of the Hot Deformation Behavior in VDM® Alloy 780 by In Situ High-Energy X-Ray Diffraction

Ni-based superalloys are indispensable for applications in demanding environments, such as the heavily stressed rotating discs in the hot sections of modern gas turbines or jet engines. In this paper, the microstructure evolution during hot deformation to mimic the forging process was investigated in the polycrystalline VDM® Alloy 780 via in situ X-ray diffraction at temperatures of 950, 1000, and 1050 °C. For the tested temperatures, the hot forming led to subgrain formation, the built-up of a texture by rotation of the matrix grains into preferred orientations, and dynamic recrystallization. The influence of the deformation was analyzed depending on the direction of the lattice plane normals to the load direction, for the first five γ-reflections in the diffraction pattern. During uniaxial compressive deformation intensity, maxima develop in the loading direction solely for the γ-(220) reflections, while intensity minima develop for the other reflections which correspond to the formation of a  fiber texture. In the transverse direction, all γ-reflections except the (220) have an increased intensity at the maximum specimen strain of 20 pct. Directly after the hot forming, three different cooling rates of 10, 100, and 1000 °C/min and their influence on the microstructure were investigated. The fast and medium cooling rates lead to low recrystallized fractions and a largely preserved deformation texture, whereas the low cooling rate leads to a high recrystallized fraction and a slight remaining texture. Additionally, the diffraction data are complemented by electron microscopy measurements

Natural attenuation of sulfonamides and metabolites in contaminated groundwater – Review, advantages and challenges of current documentation techniques

Sulfonamides are applied worldwide as antibiotics. They are emerging contaminants of concern, as their presence in the environment may lead to the spread of antibiotic resistance genes. Sulfonamides are present in groundwater systems, which suggest their persistence under certain conditions, highlighting the importance of understanding natural attenuation processes in groundwater. Biodegradation is an essential process, as degradation of sulfonamides reduces the risk of antibiotic resistance spreading. In this review, natural attenuation, and in particular assessment of biodegradation, is evaluated for sulfonamides in groundwater systems. The current knowledge level on biodegradation is reviewed, and a scientific foundation is built based on sulfonamide degradation processes, pathways, metabolites and toxicity. An overview of bacterial species and related metabolites is provided. The main research effort has focused on aerobic conditions while investigations under anaerobic conditions are lacking. The level of implementation in research is laboratory scale; here we strived to bridge towards field application and assessment, by assessing in situ approaches commonly used in monitored natural attenuation. Methods to document contaminant mass loss are assessed to be applicable for sulfonamides, while there is a lack of reference standards for metabolites. Furthermore, additional information is required on relevant metabolites in order to improve risk assessments. Based on the current knowledge on biodegradation, it is suggested to use the presence of substituent-containing metabolites from breakage of the sulfonamide bridge as specific indicators of degradation. Microbial approaches are currently available for assessment of microbial community's capacities, however, more knowledge is required on indigenous bacteria capable of degrading sulfonamides and on the impact of environmental conditions on biodegradation. Compound specific stable isotope analysis shows great potential as an additional in situ method, but further developments are required to analyse for sulfonamides at environmentally relevant levels. Finally, in a monitored natural attenuation scheme it is assessed that approaches are available that can uncover some processes related to the fate of sulfonamides in groundwater systems. Nevertheless, there are still unknowns related to relevant bacteria and metabolites for risk assessment as well as the effect of environmental settings such as redox conditions. Alongside, uncovering the fate of sulfonamides in future research, the applicability of the natural attenuation documentation approaches will advance, and provide a step towards in situ remedial concepts for the frequently detected sulfonamides

Microsensor measurements of oxygen concentration profiles, and computer-simulated concentration profiles of oxygen, ammonium and nitrate oxygen in Trichodesmium colonies

Trichodesmium is an important dinitrogen (N~2~)-fixing cyanobacterium in marine ecosystems. Recent nucleic acid analyses indicate that Trichodesmium colonies with their diverse epibionts support various nitrogen (N) transformations beyond N~2~-fixation. However, rates of these transformations and concentration gradients of N-compounds in Trichodesmium colonies remain largely unresolved. We combined isotope-tracer incubations, micro-profiling, and numeric modelling to explore carbon fixation, N-cycling processes, as well as oxygen, ammonium and nitrate concentration gradients in individual field-sampled Trichodesmium colonies. Colonies were net-autotrophic, with carbon and N~2~-fixation occurring mostly at day-time. Ten percent of the fixed N was released as ammonium after 12-hour incubations. Nitrification was not detectable but nitrate consumption was high when nitrate was added. The consumed nitrate was partly reduced to ammonium, while denitrification was insignificant. Thus, the potential N-transformation network was characterized by fixed N gain and recycling processes rather than denitrification. Oxygen concentrations within colonies were 60–200% air-saturation. Moreover, our modelling predicted steep concentration gradients, with up to 6-fold higher ammonium concentrations, and nitrate depletion in the colony centre compared to the ambient seawater. These gradients created a chemically heterogeneous microenvironment, presumably facilitating diverse microbial metabolisms in millimetre-sized Trichodesmium colonies