Headspace Sampling Research Articles

Comparison of aroma properties of infant formulas: Differences in key aroma compounds and their possible origins in processing

Aroma is an important attribute of infant formula (IF). In this study, 218 volatiles and 62 odor-active compounds were detected from IF by dynamic headspace sampling combined with comprehensive 2-dimensional gas chromatography-olfactometry-mass spectrometry. Aldehydes and ketones were determined as the most abundant odor-active compounds. Among them, the contents of pentanal and hexanal were the most abundant, while 1-octen-3-one had the highest flavor dilution factor and odor activity value in most of the IF. Sensory evaluation and electronic nose analysis showed that the skimming process, the fatty acid composition, and powdered or liquid milk base used for the production of IF may be important factors resulting in their differences in aroma profiles and compounds. These differences were assumed to be mainly ascribed to the Maillard reaction and lipid oxidation, which were largely influenced by the temperature and water activity.

Identification of pressed and extracted vegetable oils by headspace GC-MS

Edible vegetable oils are produced either by mechanical pressing or extraction. Although pressing retains the inherent flavor and nutritional value of the oil, the oil yield is low and the process expensive. Extraction methods have high oil yields, low processing costs, and economic benefits; however, No. 6 solvent, which may pose potential risks to human health, is commonly used in the extraction and cleaning process. Differentiating extracted oil containing these solvents from pressed oil, for quality control, based on visual appearance is difficult. Hence, in this study, an identification method using the characteristic components of solvent No. 6 under optimized headspace Gas chromatography-mass spectrometry (GC-MS) conditions was established. It also provided a reference for quality control of industrial production by estimating the amount of solvent present in the oil. Results showed that, in addition to five main components (2-methylpentane, 3-methylpentane, and n-hexane, Methylcyclopentane, Cyclohexane), accounting for 97% of the solvent, No. 6 solvent also contains 16 types of organic substances, such as olefins, aromatic hydrocarbons, and polycyclic aromatic hydrocarbons. Under optimized headspace GC-MS conditions (headspace sampler equilibrium temperature = 150 °C), the No. 6 solvent exhibits high linearity over a concentration range of 0.05–1 mg/kg with a correlation coefficient of 0.999 and a detection limit of 0.01 mg/kg. Pressed and extracted oils can be determined as follows: If three or fewer main components of the No. 6 solvent are detected, and the total content of No. 6 solvent is less than 0.5 mg/kg, it is a pressed oil; if four or more main components of No. 6 solvent are detected, or the total content of No. 6 solvent is ≥0.5 mg/kg, it is confirmed as an extracted oil.

Development of an analytical method to determine methyl alcohol and isopropyl alcohol in food using static headspace gas chromatography.

A method to determine methanol (MeOH) and isopropyl alcohol (IPA) was developed using static headspace sampling (HSS) with gas chromatography (GC) and gas chromatography/mass spectrometry (GC/MS). The optimized HSS-GC and HSS-GC/MS methods were validated according to the parameters. The limit of quantification (LOQ) values for MeOH analyzed by HSS-GC/MS and HSS-GC were 0.50-0.56 and 1.97mg/L, and the corresponding values for IPA were 0.14-0.21 and 1.51mg/L, respectively. Recoveries were determined by spiking sample matrices, such as vinegar and tea. MeOH and IPA showed excellent recoveries of 93.80-107.60% and 93.92-104.32% with corresponding precisions of 0.51-7.38% and 0.90-7.70%, respectively. Compared to solid-phase microextraction-GC/MS and HSS-GC, the HSS-GC/MS method showed outstanding values for limit of detection and LOQ with improved precision and accuracy. This HSS-GC/MS method was successfully used to monitor residual solvents in 100 food and functional food products.

VOC-Based Probes, a New Set of Analytical Tools to Monitor Patient Health from Blood Sample. Proof of Concept on Tracking COVID-19 Infection.

Induced volatolomics is an emerging field that holds promise for many biomedical applications including disease detection and prognosis. In this pilot study, we report the first use of a cocktail of volatile organic compounds (VOCs)-based probes to highlight new metabolic markers allowing disease prognosis. In this pilot study, we specifically targeted a set of circulating glycosidases whose activities could be associated with critical COVID-19 illness. Starting from blood sample collection, our approach relies on the incubation of VOC-based probes in plasma samples. Once activated, the probes released a set of VOCs in the sample headspace. The dynamic monitoring of the signals of VOC tracers enabled the identification of three dysregulated glycosidases in the initial phase after infection, for which preliminary machine learning analyses suggested an ability to anticipate critical disease development. This study demonstrates that our VOC-based probes are a new set of analytical tools that can provide access to biological signals until now unavailable to biologists and clinicians and which could be included in biomedical research to properly construct multifactorial therapy algorithms, necessary for personalized medicine.

Differential olfactory responses associated with host plant shift by the fruit-piercing moth, Eudocima phalonia, in the Pacific islands

ABSTRACT The fruit-piercing moth (FPM) Eudocima phalonia is widely present in the tropics, causing major damages to the citrus industry. In its ancestral distribution range, e.g. Australia, FPM develops on vines from the Menispermaceae family. But in more recently colonized islands, e.g. New Caledonia, FPM populations have shifted to new host plants of the Fabaceae family, Erythrina spp.. To understand this host shift, we studied the chemical ecology of FPM as a mechanism driving host plant acceptance. We collected volatile headspace samples of Erythrina species and Menispermaceae and compared their chemical spectra. We assessed the electrophysiological responses of FPM populations from the two countries to the plant chemical extracts and identified bioactive compounds. The volatile profiles from each species were quite different between and within each plant family. However, five compounds common across the two families triggered electrophysiological responses in both FPM populations. Those common bioactive compounds could have facilitated the host shift to completely different plant family. Furthermore, the diverging history between the two FPM populations may explain differences in electrophysiological sensitivity to other specific compounds. These results are discussed in the context of the production of a generic lure that could be attractive to all FPM populations.

Chemical Composition of Volatile Organic Compounds of an Extremely Rare and Endemic Algerian Apiaceae Species, Bunium crassifolium Batt.

Abstract Bunium crassifolium Batt. (B. crassifolium) (Apiaceae) is an extremely rare endemic species from the North East of Algeria. In this study, we extracted the volatile organic compounds (VOC) of B. crassifolium Batt. aerial parts using an Agilent G1888 network headspace sampler coupled with an Agilent 7890 GC system. The results revealed the presence of twenty-two (22) compounds, twenty (20) of which were identified as representing 97.48% of the total composition, the major components are: 44.67% of β-Cubebene, 8.82% of β-Caryophyllene, 7.04% of γ-Elemene, 4.70% of δ-Cadinene, 4.11% of γ-Cadinene, 3.77% of Ascaridole and 3.33% of β-Elemene, along with other constituents at a relatively low amount.

Synthesis and Characterization of MCM-41 Nanomaterials Containing Titanium and Application for Catalytic Oxidation of BTEX

The TiO<sub>2</sub>/MCM-41 nanomaterials were synthesized by impregnation with an excess solvent with different percentages of titanium dioxide. They were used for catalytic degradation of Benzene Toluene Ethylbenzene and Xylenes (BTEX) in the presence of hydrogen peroxide in aqueous media. The obtained materials were characterized by X-ray Diffraction, nitrogen adsorption-desorption using the BET method and Fourier Transform Infrared Spectroscopy. The nanostructured phase of the hexagonal ordered materials was obtained even after modification with titanium oxide and calcination. The characterizations have proven the effectiveness of the synthesis method used to incorporate titanium with anatase structure impregnated in the nanoporous of the MCM-41 material. Anatase is the main active phase of TiO<sub>2</sub> to oxidize organic compounds. The catalytic evaluation wascarried out in a semi-bath reactor with 20 mL of a mixture containing BTEX (100 mg/L), hydrogen peroxide (2.0 mol/L) and TiO<sub>2</sub>/MCM-41 (2.0 g/L) in aqueous media. The reactions were carried out at a temperature of 60°C for 5 hours, and the analyses were performed by gas chromatography with a photoionization detector and headspace sampler. The catalytic tests showed satisfactory results with more than 95% of conversion, where the catalyst 48%TiO<sub>2</sub>/MCM-41 presented higher performance.

Gas Phase Emissions of Volatile Organic Compounds Arising from the Application of Sunscreens.

The speciation of volatile organic compounds (VOCs) emitted from personal care products (PCPs) is complex and contributes to poor air quality and health risks to users via the inhalation exposure pathway. Detailed VOC emission profiles were generated for 26 sunscreen products; consequently, variability was observed between products, even though they were all designed for the same purpose. Some were found to contain fragrance compounds not labelled on their ingredients list. Five contaminant VOCs were identified (benzene, toluene, ethylbenzene, o-xylene, and p-xylene); headspace sampling of an additional 18 randomly selected products indicated that ethanol originating from fossil petroleum was a potential source. The gas phase emission rates of the VOCs were quantified for 15 of the most commonly emitted species using SIFT-MS. A wide range of emission rates were observed between the products. Usage estimates were made based on the recommended dose per body surface area, for which the total mass of VOCs emitted from one full-body application dose was in the range of 1.49 × 103-4.52 × 103 mg and 1.35 × 102-4.11 × 102 mg for facial application (men aged 16+; children aged 2-4). Depending on age and sex, an estimated 9.8-30 mg of ethanol is inhaled from one facial application of sunscreen.

Real-Time Monitoring of Reactions by Headspace Sampling under Ambient Mass Spectrometric Conditions

The helium-plasma (HePI) ionization mass spectrometry method was used to track the formation of reaction products and consumption of reactants by continually monitoring the vapors in the reaction headspace in real time. Two examples of the application procedure are presented here: a nucleophilic acyl substitution reaction and a 1,4-nucleophilic addition process. For the purposes of the work, a specially constructed helium-plasma ionization (HePI) source was mounted on a single-quadrupole benchtop mass spectrometer. However, any electrospray source is easily convertible to an ambient HePI source. This setup has the potential to be used in the teaching of organic and analytical chemistry laboratories, as well as for demonstrations. Because the procedure requires only the headspace of the reaction vessel to be sampled by an easily prepared Venturi suction device (pump), the experiments can be quickly set up and adapted for any available mass spectrometer equipped with an electrospray source. For sampling, students can be shown how to prepare their own Venturi pumps and conduct reactions at different temperatures.

GC/MS analysis of hypoxic volatile metabolic markers in the MDA-MB-231 breast cancer cell line.

Hypoxia in disease describes persistent low oxygen conditions, observed in a range of pathologies, including cancer. In the discovery of biomarkers in biological models, pathophysiological traits present a source of translatable metabolic products for the diagnosis of disease in humans. Part of the metabolome is represented by its volatile, gaseous fraction; the volatilome. Human volatile profiles, such as those found in breath, are able to diagnose disease, however accurate volatile biomarker discovery is required to target reliable biomarkers to develop new diagnostic tools. Using custom chambers to control oxygen levels and facilitate headspace sampling, the MDA-MB-231 breast cancer cell line was exposed to hypoxia (1% oxygen) for 24h. The maintenance of hypoxic conditions in the system was successfully validated over this time period. Targeted and untargeted gas chromatography mass spectrometry approaches revealed four significantly altered volatile organic compounds when compared to control cells. Three compounds were actively consumed by cells: methyl chloride, acetone and n-Hexane. Cells under hypoxia also produced significant amounts of styrene. This work presents a novel methodology for identification of volatile metabolisms under controlled gas conditions with novel observations of volatile metabolisms by breast cancer cells.

Aroma Characterization of Roasted Meat and Meat Substitutes Using Gas Chromatography-Mass Spectrometry with Simultaneous Selective Detection and a Dedicated Software Tool, AromaMS.

The development of healthier and more sustainable food products, such as plant-based meat substitutes (PBMSs), have received significant interest in recent years. A thorough understanding of the aroma composition can support efforts to improve the sensory properties of PBMS products and promote their consumer acceptability. Here, we developed an integrated hardware and software approach for aroma analysis of roasted food based on simultaneous analysis with three complementary detectors. Following the standard procedure of aroma headspace sampling and separation using solid-phase microextraction-gas chromatography, the column flow was split into three channels for the following detectors for the selective detection of nitrogen and sulfur (N/S)-containing compounds: an electron ionization-mass spectrometry for identification through a library search, a nitrogen-phosphorous detector, and a flame-photometric detector (FPD)/pulsed-FPD. Integration of results from the different types of detectors was achieved using a software tool, called AromaMS, developed in-house for data processing. As stipulated by the user, AromaMS performed either non-targeted screening for all volatile organic compounds (VOCs) or selective screening for N/S-containing VOCs that play a major role in the aroma experience. User-defined parameters for library matching and the retention index were applied to further eliminate false identifications. This new approach was successfully applied for comparative analysis of roasted meat and PBMS samples.

Soap application alters mosquito-host interactions

To find nutrients, mosquitoes use volatile organic compounds (VOCs) emitted by plants and animal hosts. These resources overlap in their chemical composition, and an important layer of information resides in VOCs' relative abundance in the headspace of each resource. In addition, a large majority of the human species regularly uses personal care products such as soaps and perfumes, which add plant-related VOCs to their olfactory signature. Using headspace sampling and gas chromatography-mass spectrometry, we quantified how human odor is modified by soap application. We showed that soaps alter mosquito host selection, with some soaps increasing the attractiveness of the host and some soaps reducing it. Analytical methods revealed the main chemicals associated with these changes. These results provide proof-of-concept that data on host-soap valences can be reverse-engineered to produce chemical blends for artificial baits or mosquito repellents, and evince the impact of personal care products on host selection processes.

The antimicrobial efficacy of native Australian essential oils in liquid and vapour phase against foodborne pathogens and spoilage microorganisms

Foodborne pathogens and spoilage microorganisms are a source of concern for public health and the food industry. Considering the problem of antimicrobial resistance in microbes, controlling these microorganisms using synthetic antimicrobials is challenging, thus, essential oils are a potential natural alternative. Previous studies have predominantly focussed on the antimicrobial activity of essential oils in the liquid phase. However, in this work we report on the in vitro antimicrobial activity of the liquid and vapour phases of essential oils from native Australian plants Tasmanian mountain pepper (Tasmannia lanceolata), lemon myrtle (Backhousia citriodora), as well as the common herb thyme (Thymus vulgaris) against 11 common food spoilage and pathogenic bacteria and fungi. Initial screening was conducted using the disc diffusion assay. The minimum inhibitory concentration (MIC) of the oils was determined using the broth microdilution assay. The vapour phase antimicrobial activity of the oils was assessed using an inverted petri plate assay and the vapour phase MIC (V-MIC) was quantified using a vapour diffusion assay. GC-MS was adopted to elucidate the compositional profile of the oil in liquid phase. Two extraction methods, namely solid-phase microextraction (HS-SPME) and gas tight syringe headspace sampling (HS) coupled with GC-MS were used for profiling the composition of the volatiles. The findings of this study confirmed the antimicrobial activity of the oils in both liquid and vapour phases, with lemon myrtle and thyme generally showing stronger antimicrobial activity than Tasmanian mountain pepper. The activity in liquid phase was generally higher than the volatiles. However, lemon myrtle and Tasmanian mountain pepper berry volatiles were more effective against Aspergillus niger and Saccharomyces cerevisiae, respectively, relative to the liquid phase highlighting their potential as vapour phase antifungals. In the liquid and gas phases, the major compounds in lemon myrtle were Z-citral (neral) and E-citral (geranial). Polygodial and thymol were the major compounds in Tasmanian mountain pepper and thyme in the liquid phase, respectively. However, the main compounds in their volatiles were p-cymene and γ-terpinene. In conclusion, our research indicates the essential oils' potent vapour phase activity, highlighting their potential application in gaseous diffusion-dependent food applications such as active antimicrobial food packaging.

Synthesis and investigation of silver-coated monolithic solid phase microextraction silica sorbent


 
 
 
 Monolithic solid phase microextraction silica sorbent coated with silver nanopar ticles (Ag NPs) was successfully synthesized in a small quartz capillary. The sorbent was tested in a headspace microextraction mode using various aromatic compounds followed by gas chromatography analysis. Due to the π-π electronic interaction between analytes aromatic systems and silver particles immobilized on the sorbent surface, the analytes were successfully extracted from a sample headspace and determined by gas chromatographic analysis.
 
 
 

A high-throughput atomic emission analyzer for simultaneous field detection of dissolved inorganic and organic carbon in seawater and lake water

Dissolved inorganic carbon (DIC) and dissolved organic carbon (DOC) are two important indicators of global carbon cycle. However, there are no portable analyzers available to simultaneously accomplish high-throughput field detection of them in the same sample. Herein, a simple analyzer comprising a dual-mode reactor to accomplish both chemical vapor generation and headspace sampling, and a miniature point discharge optical emission spectrometer (μPD-OES) was developed for simultaneous and high-throughput detection of DIC and DOC in seawater and lake water. Phosphoric acid and persulfate were successively injected into sample solutions to convert DIC and DOC to CO2 under the conditions of magnetic stirring and UV irradiation, respectively. Subsequently, the generated CO2 was swept into the μPD-OES for quantitation of DIC and DOC via monitoring carbon atomic emission at 193.0 nm. Under optimal conditions, limits of detection for DIC and DOC (as C) were both 0.01 mg L−1 with relative standard deviations (n = 20) better than 5% and sample throughput of 80 samples per hour. Compared to conventional analyzers, the proposed instrument provides the advantages of high throughput, compactness, low energy consumption and eliminates expensive instruments. The accuracy of the system was validated by simultaneous determination of DIC and DOC in various water samples in laboratory and field environments.

GC-MS Profiling of Reproductive Stage Withania somnifera for Antimicrobial and Anticancer Phytochemicals

Withanias omnifera also known as Indian ginseng is commonly found in India and other Southeast Asian countries. Various parts of this plant have been used as herbal medicine to treat a variety of diseases. However, there is a lacuna in the profiling of phytochemical constituents present in the different parts of the plant at reproductive stage. To identify phytochemicals present in the methanolic extracts of leaf, root, and stem parts of W. somnifera at reproductive stage using GC-MS analysis. Methods: The airdried parts of plant (leaf, stem and root) were extracted with methanol and concentrated under reduced pressure at 40°C using a rotary evaporator. The GCMSQP2010, Shimadzu, Kyoto, Japan with headspace sampler (AOC-20s) and autoinjector (AOC-20i), was used for sample analysis. The phytochemicals were identified with the database provided by National Institute Standard and Technology (NIST11LIB). The GC-MS analysis of leaf, root, and stem methanolic extracts of W. somnifera, revealed a total of eighty-two unique phytochemical peaks in the reproductive stage of the plant. Phytochemicals with antimicrobial and anticancer properties were identified in all the parts. In leaf, 2-pentanone, 5-chloro- was found to be most abundant and 2,5-dimethoxy-4-propoxy-. beta.-methyl-.beta.-nitrostyrene least abundant with antimicrobial nature, whereas, benzene, 1,1'-(1,2-ethenediyl)bis[2-methyl- was found to be most abundant and dibenzo[a,e]cyclooctene, 5,6,11,12-tetrahydro- least with anticancer property. In roots, the most abundant was benzoic acid, 3-methyl-2-trimethylsilyloxy-, trimethylsilyl ester and tris(trimethylsilyl)hydroxylamine the least abundant were identified to be antimicrobial, whereas high abundance uleine and low abundance 2-{4-[2-(4-methoxymethylphenyl)vinyl]phenyl}propan-2-olwere identified to be anticancer. In stem, acetohydroxamic acid was found to be most abundant and trans2,3,6-trimethoxy-b-methyl-b-nitrostyrene least abundant for antimicrobial nature, whereas 3-acetoxy-2,3'-bibenzo[b]thiophene was found to be anticancer phytochemical. In this study, phytochemicals with antimicrobial and anticancer properties were identified in leaf, root and stem parts of W. somnifera at reproductive stage.

Liquid Biopsy-Based Volatile Organic Compounds from Blood and Urine and Their Combined Data Sets for Highly Accurate Detection of Cancer.

Liquid biopsy is seen as a prospective tool for cancer screening and tracking. However, the difficulty lies in effectively sieving, isolating, and overseeing cancer biomarkers from the backdrop of multiple disrupting cells and substances. The current study reports on the ability to perform liquid biopsy without the need to physically filter and/or isolate the cancer cells per se. This has been achieved through the detection and classification of volatile organic compounds (VOCs) emitted from the cancer cells found in the headspace of blood or urine samples or a combined data set of both. Spectrometric analysis shows that blood and urine contain complementary or overlapping VOC information on kidney cancer, gastric cancer, lung cancer, and fibrogastroscopy subjects. Based on this information, a nanomaterial-based chemical sensor array in conjugation with machine learning as well as data fusion of the signals achieved was carried out on various body fluids to assess the VOC profiles of cancer. The detection of VOC patterns by either Gas Chromatography-Mass Spectrometry (GC-MS) analysis or our sensor array achieved >90% accuracy, >80% sensitivity, and >80% specificity in different binary classification tasks. The hybrid approach, namely, analyzing the VOC datasets of blood and urine together, contributes an additional discrimination ability to the improvement (>3%) of the model's accuracy. The contribution of the hybrid approach for an additional discrimination ability to the improvement of the model's accuracy is examined and reported.

Urinary bio-monitoring of aromatic amine derivatives by new needle trap device packed with the multi-component adsorbent

Aromatic amines are a large group of chemical compounds that have attracted the attention of researchers due to their toxicity and carcinogenicity. This study aimed to develop an efficient method for sampling and analysis of aromatic amines (Aniline, N, N-dimethylaniline, 2-chloroaniline, and 3-chloroaniline) from the vapour phase (headspace) of urine samples. For the implementation of this plan, a needle trap device packed with the three-component adsorbent consisting of nano-Hydroxy Apatite (nHA), Zeolite (Ze), and Metal–Organic Framework (MOF) equipped with GC-FID was employed for the first phase. Examination of the prepared adsorbents was performed by FT-IR, PXRD, and FE-SEM techniques. The optimal value of considerable parameters such as time and temperature of extraction, salt content, and pH were established using the Response Surface Methodology-Central Composite Design (RMS-CCD) method. In this way, the optimal extraction of targeted analytes was accomplished in 41 min at 41 °C with NaCl content of 33.0% (w/v) and pH: 13.0, respectively. Also, the repeatability and reproducibility of the method were calculated to be in the range of 2.2–7.1% and 3.9–8.1%, respectively, which indicates the acceptable precision of the method. Also, the limit of detection (LOD) and limit of quantification (LOQ) were determined in the range of 0.3–32.0 ng.L−1 and 0.8–350.0 ng.L−1, respectively, which proves the high sensitivity of the proposed method. Furthermore, the recovery percent of the extracted analytes was concluded in the range of 97.0–99.0% after 6 and 30 days of the sampling and storage at 25 °C and 4 °C, respectively. Finally, the designed procedure was employed in the analysis of the above-mentioned aromatic amines in the real urine samples. The achieved results illustrate that the three-component absorbent system (nHA;Ze;MOF@NTD) can be introduced as an efficient, fast-response, sensitive, and versatile procedure for trace analysis of the different aromatic amine compounds in public and occupational health.

Design of an Online Electrochemical Mass Spectrometry System to Study Gas Evolution from Cells with Lean and Volatile Electrolytes.

Gas evolution in high-energy Li-ion batteries remains a pervasive problem for a multitude of chemistries, jeopardizing the electrochemical performance and safety for consumers of electric vehicles. Many electrode-electrolyte degradation processes evolve gasses that may be detected in-situ with online electrochemical mass spectrometry (OEMS). In this work, details are provided for the setup and validation of an OEMS system that operates well under lean and volatile electrolyte conditions. Quite notably, the OEMS cells with only 40µL of electrolyte and intermittent headspace sampling exhibit comparable electrochemical performance to flooded coin-cells. It is demonstrated that the onset time, shape, and magnitude of the gas evolution profiles calculated from mass spectrometer measurements match well to a known pressure reference through the use of an empirically determined fraction of removal. The off-gassing characteristics from a set of layered-oxide materials, NMC532, NMC811, and LNO, are used to further validate the OEMS setup against the literature. It is shown that many of the features present in the OEMS curves for equivalent systems from other groups are captured by this OEMS system. At an upper cut-off voltage of 4.4V, LNO exhibits an intense release of CO2 , O2 , and CO gas relative to NMC532 and NMC811.

Abrasion of sedimentary rocks as a source of hydrogen peroxide and nutrients to subglacial ecosystems

Abstract. Glaciers and ice sheets are renowned for their abrasive power, yet little is known of the mechanochemical reactions which are initiated by abrasion in these environments and their effect on subglacial biogeochemistry. Here, we use sedimentary rocks representative of different subglacial environments and from a previously glaciated terrain, along with subglacial sediments, to investigate the potential for subglacial erosion to generate H2O2 and to release bio-utilisable organic carbon and nutrients (N, Fe). Samples were crushed using a ball mill, water was added to rock powders within gastight vials, and samples were incubated in the dark at 4 ∘C. Headspace and water samples were taken immediately after the addition of water and then again after 5 and 25 h. Samples generated up to 1.5 µmol H2O2 g−1. The total sulfur content, a proxy for the sulfide content, did not correlate with H2O2 generation, suggesting that the pyrite content was not the sole determinant of net H2O2 production. Other factors including the presence of carbonates, Fe-driven Fenton reactions and the pH of the solution were also likely to be important in controlling both the initial rate of production and subsequent rates of destruction of H2O2. Further, we found that erosion can provide previously unaccounted sources of bio-utilisable energy substrates and nutrients, including up to 880 nmol CH4 g−1, 680 nmol H2 g−1, volatile fatty acids (up to 1.7 µmol acetate g−1) and 8.2 µmolNH4+g-1 to subglacial ecosystems. These results highlight the potentially important role that abrasion plays in providing nutrient and energy sources to subglacial microbial ecosystems underlain by sedimentary rocks.