Frequency of use of household products containing VOCs and indoor atmospheric concentrations in homes.

Volatile organic compounds (VOCs) are a key class of atmospheric emission released from highly complex petrochemical, transport and solvent sources both outdoors and indoors. This study established the concentrations and speciation of VOCs in 60 homes (204 individuals, 360 × 72 h samples, 40 species) in summer and winter, along with outdoor controls. Self-reported daily statistics were collected in each home on the use of cleaning, household and personal care products, all of which are known to release VOCs. Frequency of product use varied widely: deodorants: 2.9 uses home per day; sealant-mastics 0.02 uses home per day. The total concentration of VOCs indoors (range C2-C10) was highly variable between homes e.g. range 16.6-8150 µg m-3 in winter. Indoor concentrations of VOCs exceeded outdoor for 84% of households studied in summer and 100% of homes in winter. The most abundant VOCs found indoors in this study were n-butane (wintertime range: 1.5-4630 µg m-3), likely released as aerosol propellant, ethanol, acetone and propane. The cumulative use VOC-containing products over multiday timescales by occupants provided little predictive power to infer 72 hour averaged indoor concentrations. However, there was weak covariance between the cumulative usage of certain products and individual VOCs. From a domestic emissions perspective, reducing the use of hydrocarbon-based aerosol propellants indoors would likely have the largest impact.

An Automated Methodology for Non-targeted Compositional Analysis of Small Molecules in High Complexity Environmental Matrices Using Coupled Ultra Performance Liquid Chromatography Orbitrap Mass Spectrometry.

The life-critical matrices of air and water are among the most complex chemical mixtures that are ever encountered. Ultrahigh-resolution mass spectrometers, such as the Orbitrap, provide unprecedented analytical capabilities to probe the molecular composition of such matrices, but the extraction of non-targeted chemical information is impractical to perform via manual data processing. Automated non-targeted tools rapidly extract the chemical information of all detected compounds within a sample dataset. However, these methods have not been exploited in the environmental sciences. Here, we provide an automated and (for the first time) rigorously tested methodology for the non-targeted compositional analysis of environmental matrices using coupled liquid chromatography-mass spectrometric data. First, the robustness and reproducibility was tested using authentic standards, evaluating performance as a function of concentration, ionization potential, and sample complexity. The method was then used for the compositional analysis of particulate matter and surface waters collected from worldwide locations. The method detected >9600 compounds in the individual environmental samples, arising from critical pollutant sources, including carcinogenic industrial chemicals, pesticides, and pharmaceuticals among others. This methodology offers considerable advances in the environmental sciences, providing a more complete assessment of sample compositions while significantly increasing throughput.

Influence of the Sea Surface Microlayer on Oceanic Iodine Emissions.

The influence of organic compounds on iodine (I2) emissions from the O3 + I- reaction at the sea surface was investigated in laboratory and modeling studies using artificial solutions, natural subsurface seawater (SSW), and, for the first time, samples of the surface microlayer (SML). Gas-phase I2 was measured directly above the surface of liquid samples using broadband cavity enhanced absorption spectroscopy. I2 emissions were consistently lower for artificial seawater (AS) than buffered potassium iodide (KI) solutions. Natural seawater samples showed the strongest reduction of I2 emissions compared to artificial solutions with equivalent [I-], and the reduction was more pronounced over SML than SSW. Emissions of volatile organic iodine (VOI) were highest from SML samples but remained a negligible fraction (<1%) of the total iodine flux. Therefore, reduced iodine emissions from natural seawater cannot be explained by chemical losses of I2 or hypoiodous acid (HOI), leading to VOI. An interfacial model explains this reduction by increased solubility of the I2 product in the organic-rich interfacial layer of seawater. Our results highlight the importance of using environmentally representative concentrations in studies of the O3 + I- reaction and demonstrate the influence the SML exerts on emissions of iodine and potentially other volatile species.

Unexpectedly high concentrations of monoterpenes in a study of UK homes.

The abundance of volatile organic compounds (VOCs) found in homes depends on many factors such as emissions, ventilation and the oxidative environment and these are evolving over time, reflecting changes in chemical use, behaviour and building design/materials. The concentrations of VOCs in 25 UK homes of varying ages, design and occupancy were quantified using continuous indoor air sampling over five days. Air was collected through low flow (1 mL min-1) constant flow restrictors into evacuated 6 L internally silica-treated canisters until the canisters reached atmospheric pressure. This was followed by thermal desorption-gas chromatography and high mass accuracy time-of-flight mass spectrometry (TD-GC-TOF/MS). A fully quantitative analysis was performed on the eight most abundant hydrocarbon-based VOCs found. Despite differences in building characteristics and occupant numbers 94% of the homes had d-limonene or α-pinene as the most abundant VOCs. The variability seen across the 25 homes in concentrations of monoterpenes indoors was considerably greater than that of species such as isoprene, benzene, toluene and xylenes. The variance in VOCs indoors appeared to be strongly influenced by occupant activities such as cleaning with 5-day average concentrations of d-limonene ranging from 18 µg m-3 to over 1400 µg m-3, a peak domestic value that is possibly the highest yet reported in the literature.

Protein sequences bound to mineral surfaces persist into deep time.

Proteins persist longer in the fossil record than DNA, but the longevity, survival mechanisms and substrates remain contested. Here, we demonstrate the role of mineral binding in preserving the protein sequence in ostrich (Struthionidae) eggshell, including from the palaeontological sites of Laetoli (3.8 Ma) and Olduvai Gorge (1.3 Ma) in Tanzania. By tracking protein diagenesis back in time we find consistent patterns of preservation, demonstrating authenticity of the surviving sequences. Molecular dynamics simulations of struthiocalcin-1 and -2, the dominant proteins within the eggshell, reveal that distinct domains bind to the mineral surface. It is the domain with the strongest calculated binding energy to the calcite surface that is selectively preserved. Thermal age calculations demonstrate that the Laetoli and Olduvai peptides are 50 times older than any previously authenticated sequence (equivalent to ~16 Ma at a constant 10°C).

Insights into the Formation and Evolution of Individual Compounds in the Particulate Phase during Aromatic Photo-Oxidation.

Secondary organic aerosol (SOA) is well-known to have adverse effects on air quality and human health. However, the dynamic mechanisms occurring during SOA formation and evolution are poorly understood. The time-resolved SOA composition formed during the photo-oxidation of three aromatic compounds, methyl chavicol, toluene and 4-methyl catechol, were investigated at the European Photoreactor. SOA was collected using a particle into liquid sampler and analyzed offline using state-of-the-art mass spectrometry to produce temporal profiles of individual photo-oxidation products. In the photo-oxidation of methyl chavicol, 70 individual compounds were characterized and three distinctive temporal profile shapes were observed. The calculated mass fraction (Ci,aer/COA) of the individual SOA compounds showed either a linear trend (increasing/decreasing) or exponential decay with time. Substituted nitrophenols showed an exponential decay, with the nitro-group on the aromatic ring found to control the formation and loss of these species in the aerosol phase. Nitrophenols from both methyl chavicol and toluene photo-oxidation experiments showed a strong relationship with the NO2/NO (ppbv/ppbv) ratio and were observed during initial SOA growth. The location of the nitrophenol aromatic substitutions was found to be critically important, with the nitrophenol in the photo-oxidation of 4-methyl catechol not partitioning into the aerosol phase until irradiation had stopped; highlighting the importance of studying SOA formation and evolution at a molecular level.