Environmental contextAerosol water-soluble organic carbon is a complex mixture of thousands of organic compounds which may have a significant influence on the climate-relevant properties of atmospheric aerosols. Using ultrahigh resolution mass spectrometry, more than 4000 individual molecular formulas were identified in non-urban aerosol water-soluble organic carbon. A significant fraction of the assigned molecular formulas were matched to assigned molecular formulas of laboratory generated secondary organic aerosols. AbstractWater-soluble organic carbon (WSOC) is a complex mixture of thousands of organic compounds which may have significant influence on the climate-relevant properties of atmospheric aerosols. An improved understanding of the molecular composition of WSOC is needed to evaluate the effect of aerosol composition upon aerosol physical properties. In this work, ultrahigh-resolution Fourier transform–ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterise aerosol WSOC collected during the summer of 2010 at the Storm Peak Laboratory (3210 m ASL) near Steamboat Springs, CO. Approximately 4000 molecular formulas were assigned in the mass range of 100–800 Da after negative-ion electrospray ionisation and more than 50 % of them contained nitrogen or sulfur. The double bond equivalents (DBEs) of the molecular formulas were inversely proportional to the O : C ratio, despite a relatively constant H : C ratio of ~1.5. Despite the range of DBE values, the elemental ratios and the high number of oxygen atoms per formula indicate that a majority of the compounds are aliphatic to olefinic in nature. These trends indicate significant non-oxidative accretion reaction pathways for the formation of high molecular weight WSOC components. In addition, a significant number of molecular formulas assigned in this work matched those previously identified as secondary organic aerosol components of monoterpene and sesquiterpene ozonolysis.

Salinity has been reported to influence the water solubility of organic chemicals entering marine ecosystems. However, limited data are available on salinity impacts for chemicals potentially entering seawater. Impacts on water solubility would correspondingly impact chemical sorption as well as overall bioavailability and exposure estimates used in the regulatory assessment. The pesticides atrazine, fipronil, bifenthrin, and cypermethrin, as well as the crude oil constituent dibenzothiophene together with 3 of its alkyl derivatives, all have different polarities and were selected as model compounds to demonstrate the impact of salinity on their solubility and partitioning behavior. The n-octanol/water partition coefficient (K ) was measured in both distilled-deionized water and artificial seawater (3.2%). All compounds had diminished solubility and increased K values in artificial seawater compared with distilled-deionized water. A linear correlation curve estimated salinity may increase the log K value by 2.6%/1 log unit increase in distilled water (R = 0.97). Salinity appears to generally decrease the water solubility and increase the partitioning potential. Environmental fate estimates based on these parameters indicate elevated chemical sorption to sediment, overall bioavailability, and toxicity in artificial seawater. These dramatic differences suggest that salinity should be taken into account when exposure estimates are made for marine organisms. Environ Toxicol Chem 2017;36:2274-2280. © 2017 SETAC.

Endocrine disrupting compounds (EDCs) are now widely established to be present in the environment at concentrations capable of affecting wild organisms. Although many studies have been conducted in fish, less is known about effects in invertebrates such as decapod crustaceans. Decapods are exposed to low concentrations of EDCs that may cause infertility, decreased growth, and developmental abnormalities. The objective herein was to evaluate effects of fipronil and its photodegradation product fipronil desulfinyl. Fipronil desulfinyl was detected in the eggs of the decapod Callinectes sapidus sampled off the coast of South Carolina. As such, to examine specific effects on C. sapidus exposed in early life, we exposed laboratory-reared juveniles to fipronil and fipronil desulfinyl for 96h at three nominal concentrations (0.01, 0.1, 0.5μg/l) and two different salinities (10, 30ppt). The size of individual crabs (weight, carapace width) and the expression of several genes critical to growth and reproduction were evaluated. Exposure to fipronil and fipronil desulfinyl resulted in significant size increases in all treatments compared to controls. Levels of expression for vitellogenin (Vtg), an egg yolk precursor, and the ecdysone receptor (EcR), which binds to ecdysteroids that control molting, were inversely correlated with increasing fipronil and fipronil desulfinyl concentrations. Effects on overall growth and on the expression of EcR and Vtg differ depending on the exposure salinity. The solubility of fipronil is demonstrated to decrease considerably at higher salinities. This suggests that fipronil and its photodegradation products may be more bioavailable to benthic organisms as salinity increases, as more chemical would partition to tissues. Our findings suggest that endocrine disruption is occurring through alterations to gene expression in C. sapidus populations exposed to environmental levels of fipronil, and that effects may be dependent upon the salinity at which exposure occurs.

Dicloran appears to be a model pesticide for investigating photodegradation processes in surface waters. Photodegradation processes are particularly relevant to this compound as it is applied to crops grown in proximity to freshwater and marine ecosystems. The photodegradation of dicloran under simulated sunlight was measured in distilled water, artificial seawater, phosphate buffer, and filter-sterilized estuarine water to determine its half-life, degradation rate, and photodegradation products. The half-life was approximately 7.5 h in all media. There was no significant difference in the rate of degradation between distilled water and artificial seawater for dicloran. For the intermediate products, a higher concentration of 2-chloro-1,4-benzoquinone was measured in artificial seawater versus distilled water, while a slightly higher concentration of 1,4-benzoquinone was measured in distilled water versus artificial seawater. The detection of chloride and nitrate ions after 2 h of light exposure suggests photonucleophilic substitution contributes to the degradation process. Differences in product distributions between water types suggest that salinity impacts on chemical degradation may need to be addressed in chemical exposure assessments.

Environmental context The organic fraction of atmospheric aerosols is a complex mixture of thousands of species, which play an important role in many atmospheric processes, such as absorbing and scattering solar radiation. We analysed the water-soluble organic fraction of ambient aerosol samples, and quantified over 45 carboxylic acids, sugars, sugar anhydrides and sugar alcohols. The presence of fairly high concentrations of sugars and sugar-alcohols suggests a significant biological input (e.g. pollen, fungi and bacteria) to the water-soluble organic fraction of non-urban aerosols. Abstract Water-soluble organic constituents of PM2.5 aerosol (particulate matter with an aerodynamic diameter ≤2.5µm) have not been well characterised so far. The goal of this work was to perform quantitative analysis of individual water-soluble organic species in aerosol samples collected in July of 2010 at the Storm Peak Laboratory (3210m above sea level) located in the Colorado Park Range (Steamboat Springs, CO, USA). Aqueous extracts were combined into six composites and analysed for organic carbon (OC), water-soluble organic carbon (WSOC), water-insoluble OC, inorganic ions, organic acids, lignin derivatives, sugar-alcohols, sugars and sugar-anhydrates. Analysis of higher molecular weight water-soluble organics was done using ultrahigh resolution mass spectrometry. Approximately 2400 positive and 4000 negative ions were detected and assigned to monoisotopic molecular formulae in the mass range of 100–800Da. The higher number of negative ions reflects a predominant presence of highly oxidised organic compounds. Individual identified organic species represented up to 30% of the water-soluble organic mass (WSOM). The WSOM fractions of the low molecular weight organic acids, sugars and sugar alcohols were 3–12%, 1.0–16% and 0.4–1.9%. Significant amounts of arabitol, mannitol and oxalic acid are most likely associated with airborne fungal spores and conidia that were observed on the filters using high resolution electron microscopy. Overall, higher concentrations of sugars (glucose, sucrose, fructose etc.) in comparison with biomass burning tracer levoglucosan indicate that a significant mass fraction of WSOC is related to airborne biological species.