Tracking abiotic transformation of 1,1,1-trichloroethane to 1,1-dichloroethylene in contaminated groundwater on a national scale.

1,1,1-trichloroethane (TCA) is a chlorinated aliphatic compound that was increasingly applied as a replacement for trichloroethylene. TCA can simultaneously follow two abiotic degradation processes: hydrolysis and dehydrochlorination, where the latter lead to the formation of a relatively recalcitrant product 1,1-dichloroethylene (DCE). The abiotic processes are relatively rapid and can be assessed based on the ratio between TCA and DCE.

An investigation of soil and groundwater metagenomes for genes encoding soluble and particulate methane monooxygenase, toluene-4-monoxygenase, propane monooxygenase and phenol hydroxylase.

Soil and groundwater were investigated for the genes encoding soluble and particulate methane monooxygenase/ammonia monooxygenase (sMMO, pMMO/AMO), toluene 4-monooxygenase (T4MO), propane monooxygenase (PMO) and phenol hydroxylase (PH). The objectives were (1) to determine which subunits were present, (2) to examine the diversity of the phylotypes associated with the biomarkers and (3) to identify which metagenome associated genomes (MAGs) contained these subunits. All T4MO and PH subunits were annotated in the groundwater metagenomes, while few were annotated in the soil metagenomes.

Microbial hydrolysis of atrazine in contaminated groundwater.

Degradation of the widespread herbicide atrazine has been intensively studied in soils, while its degradation in groundwater has received less attention. This work studied atrazine degradation in contaminated groundwater adjacent to its production plant. The degradation potential was first explored in groundwater enrichment cultures.

Optimization of compound-specific chlorine stable isotope analysis of chloroform using the Taguchi design of experiments.

Rationale: Chloroform, a probable human carcinogen, is commonly detected in various concentration levels in many surface water and groundwater sources. Compound-specific chlorine stable isotope analysis (Cl-CSIA) is significant in investigating the fate of chlorinated contaminants in the environment. Analytical conditions should, however, be thoroughly examined for any isotopic fractionation.

Multi-elemental C-Br-Cl isotope analysis for characterizing biotic and abiotic transformations of 1-bromo-2-chloroethane (BCE).

Multi-elemental C-Br-Cl compound-specific isotope analysis was applied for characterizing abiotic and biotic degradation of the environmental pollutant 1-bromo-2-chloroethane (BCE). Isotope effects were determined in the model processes following hydrolytic dehalogenation and dihaloelimination pathways as well as in a microcosm experiment by the microbial culture from the contaminated site. Hydrolytic dehalogenation of BCE under alkaline conditions and by DhaA enzyme resulted in similar dual isotope slopes (Ʌ 21.

Isotope Fractionation (δC, δN) in the Microbial Degradation of Bromoxynil by Aerobic and Anaerobic Soil Enrichment Cultures.

Bromoxynil is an increasingly applied nitrile herbicide. Under aerobic conditions, hydration, nitrilation, or hydroxylation of the nitrile group commonly occurs, whereas under anaerobic conditions reductive dehalogenation is common. This work studied the isotope effects associated with these processes by soil cultures.

Isotope analysis method for the herbicide bromoxynil and its application to study photo-degradation processes.

Bromoxynil is an increasingly applied nitrile herbicide used for post-emergent control of annual broadleaved weeds. Compound-specific isotope analysis (CSIA) of the compound is of interest for studying its environmental fate, yet is challenging following its polar nature. We present a CSIA method for bromoxynil that includes offline thin-layer chromatography purification followed by an elemental analyzer isotope ratio mass spectrometer (EA-IRMS).

Potential for co-metabolic oxidation of TCE and evidence for its occurrence in a large-scale aquifer survey.

Trichloroethylene (TCE) is a groundwater pollutant that is prevalent worldwide. In contaminated groundwater, TCE can be biodegraded following either reductive dechlorination or aerobic co-metabolic oxidation. However, since the co-metabolic process is not accompanied by indicative and easily detectable transformation products, little is known about its prominence in the environment.

Variable carbon and chlorine isotope fractionation in TCE co-metabolic oxidation.

Identifying co-metabolic TCE oxidation in polluted groundwater is challenging due to lack of indicative by-products. This challenge may theoretically be resolved if the oxidation process can be characterized by a distinct dual isotope enrichment. In this work, we aimed to explore the carbon and chlorine isotope effects associated with TCE oxidation by a variety of oxygenases.

Toward Improved Accuracy in Chlorine Isotope Analysis: Synthesis Routes for In-House Standards and Characterization via Complementary Mass Spectrometry Methods.

Increasing applications of compound-specific chlorine isotope analysis (CSIA) emphasize the need for chlorine isotope standards that bracket a wider range of isotope values in order to ensure accurate results. With one exception (USGS38), however, all international chlorine isotope reference materials (chloride and perchlorate salts) fall within the narrow range of one per mille. Furthermore, compound-specific working standards are required for chlorine CSIA but are not available for most organic substances.

Derivatization-free method for compound-specific isotope analysis of nonexchangeable hydrogen of 4-bromophenol.

Rationale: Compound-specific isotope analysis (CSIA) is a valuable tool in environmental chemistry and in other fields of science. Currently, hydrogen CSIA of polar compounds containing exchangeable hydrogen is uncommon. To extend the scope of CSIA applications, we present an alternative method of analysis, bypassing the typical step of derivatization.

Degradation of 4-bromophenol by Ochrobactrum sp. HI1 isolated from desert soil: pathway and isotope effects.

Anthropogenic activities have introduced elevated levels of brominated phenols to the environment. These compounds are associated with toxic and endocrine effects, and their environmental fate is of interest. An aerobic strain Ochrobactrum sp.

Microbial degradation of the brominated flame retardant TBNPA by groundwater bacteria: laboratory and field study.

In the present study, the biodegradation of the brominated flame retardant tribromoneopentylalcohol (TBNPA) by a groundwater enrichment culture was investigated using a dual carbon ((13)C/(12)C)- bromine ((81)Br/(79)Br) stable isotope analysis. An indigenous aerobic bacterial consortium was enriched from the polluted groundwater underlying an industrial site in the northern Negev Desert, Israel, where TBNPA is an abundant pollutant. Aerobic biodegradation was shown to be rapid, with complete debromination within a few days, whereas anaerobic biodegradation was not observed.

Chlorine isotope effects from isotope ratio mass spectrometry suggest intramolecular C-Cl bond competition in trichloroethene (TCE) reductive dehalogenation.

Chlorinated ethenes are prevalent groundwater contaminants. To better constrain (bio)chemical reaction mechanisms of reductive dechlorination, the position-specificity of reductive trichloroethene (TCE) dehalogenation was investigated. Selective biotransformation reactions (i) of tetrachloroethene (PCE) to TCE in cultures of Desulfitobacterium sp.

Reductive dechlorination of TCE by chemical model systems in comparison to dehalogenating bacteria: insights from dual element isotope analysis (13C/12C, 37Cl/35Cl).

Chloroethenes like trichloroethene (TCE) are prevalent environmental contaminants, which may be degraded through reductive dechlorination. Chemical models such as cobalamine (vitamin B12) and its simplified analogue cobaloxime have served to mimic microbial reductive dechlorination. To test whether in vitro and in vivo mechanisms agree, we combined carbon and chlorine isotope measurements of TCE.

Insight on RDX degradation mechanism by Rhodococcus strains using 13C and 15N kinetic isotope effects.

The explosive Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is known to be degraded aerobically by various isolates of the Rhodococcus species, with denitration being the key step, mediated by Cytochrome P450. Our study aimed at gaining insight into the RDX degradation mechanism by Rhodococcus species and comparing isotope effects associated with RDX degradation by distinct Rhodococcus strains. For these purposes, enrichment in (13)C and (15)N isotopes throughout RDX denitration was studied for three distinct Rhodococcus strains, isolated from soil and groundwater in an RDX-contaminated site.

Kinetic bromine isotope effect: example from the microbial debromination of brominated phenols.

The increasing use of kinetic isotope effects for environmental studies has motivated the development of new compound-specific isotope analysis techniques for emerging pollutants. Recently, high-precision bromine isotope analysis in individual brominated organic compounds was proposed, by the coupling of gas chromatography to a multi-collector inductively coupled plasma mass spectrometer using strontium as an external spike for instrumental bias correction. The present study, for the first time, demonstrates an application of this technique for determining bromine kinetic isotope effects during biological reaction, focusing on the reductive debromination of brominated phenols under anaerobic conditions.

Current challenges in compound-specific stable isotope analysis of environmental organic contaminants.

Compound-specific stable-isotope analysis (CSIA) has greatly facilitated assessment of sources and transformation processes of organic pollutants. Multielement isotope analysis is one of the most promising applications of CSIA because it even enables distinction of different transformation pathways. This review introduces the essential features of continuous-flow isotope-ratio mass spectrometry (IRMS) and highlights current challenges in environmental analysis as exemplified for the isotopes of nitrogen, hydrogen, chlorine, and oxygen.

Compound-specific chlorine isotope analysis: a comparison of gas chromatography/isotope ratio mass spectrometry and gas chromatography/quadrupole mass spectrometry methods in an interlaboratory study.

Chlorine isotope analysis of chlorinated hydrocarbons like trichloroethylene (TCE) is of emerging demand because these species are important environmental pollutants. Continuous flow analysis of noncombusted TCE molecules, either by gas chromatography/isotope ratio mass spectrometry (GC/IRMS) or by GC/quadrupole mass spectrometry (GC/qMS), was recently brought forward as innovative analytical solution. Despite early implementations, a benchmark for routine applications has been missing.

Isolation and characterization of RDX-degrading Rhodococcus species from a contaminated aquifer.

Groundwater contamination by the explosive hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a global problem. Israel's coastal aquifer was contaminated with RDX. This aquifer is mostly aerobic and we therefore sought aerobic bacteria that might be involved in natural attenuation of the compound in the aquifer.

Small and reproducible isotope effects during methylation with trimethylsulfonium hydroxide (TMSH): a convenient derivatization method for isotope analysis of negatively charged molecules.

Negatively charged analytes must be derivatized prior to gas chromatography-isotope ratio mass spectrometry (GC-IRMS), with stringent control of isotope fractionation. Current methods require offline sample preparation. This study tests for the first time trimethylsulfonium hydroxide (TMSH) as online methylation agent prior to isotope analysis, addressing the herbicides bentazone and MCPA.

Quantifying RDX biodegradation in groundwater using delta15N isotope analysis.

Isotope analysis was used to examine the extent of hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) biodegradation in groundwater along a ca. 1.35-km contamination plume.

Compound-specific isotope analysis of RDX and stable isotope fractionation during aerobic and anaerobic biodegradation.

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a common contaminant at explosives production sites. Here, we report on the use of compound-specific isotope analysis of RDX to obtain delta(15)N and delta(18)O enrichment factors during biodegradation in batch cultures. A new preparation method has been developed based on RDX purification using thin-layer chromatography.

Simple digestion procedure followed by the azomethine-H method for accurate boron analysis and discrimination between its fractions in wastewater and soils.

Excess boron is a growing environmental problem. It often affects agricultural yields, where reuse of wastewater for irrigation is practiced. This problem raises the need for reliable, simple and economical methods to monitor boron concentrations in wastewater and soil extracts.

Dilution tests in a low-permeability fractured aquifer: matrix diffusion effect.

A point dilution test is commonly used in single-borehole tracer experiments designed to determine the Darcy velocity of a formation. This method is based on the concept that, in a borehole, a tracer's concentration declines as a consequence of the water flux. Based on theoretical simulations and field observations, this study indicates that for low-permeability, yet highly porous fractured formations, the common practice of excluding the effect of diffusive mass flux between the dissolved tracer within the borehole and the surrounding matrix may lead to significant errors in the assessment of the Darcy velocity.