Quantification and physical analysis of nanoparticle emissions from a marine engine using different fuels and a laboratory wet scrubber.

A marine test-bed diesel engine was used to study how international fuel sulfur content (FSC) regulations and wet scrubbing can affect physical properties of submicron exhaust particles. Particle size distributions, particle number and mass emission factors as well as effective densities of particulate emissions were measured for three distillate fuels of varying FSC and a laboratory wet scrubber. While particle number concentrations were reduced by up to 9% when switching to low FSC fuels, wet scrubbing led to increased ultrafine particulate emissions (<30 nm). Exhaust processed through the scrubber was also found to have particles with greater effective densities, a result that directly contradicts the particulate characteristics of low FSC fuel emissions. The results demonstrate that alternative pathways to comply with marine FSC regulations can have opposing effects and thus may have very different implications for important atmospheric processes. The relevance for air quality, and the potential implications for cloud and climate interactions are discussed.

Effects of seawater scrubbing on a microplanktonic community during a summer-bloom in the Baltic Sea.

The International Maritime Organization (IMO) has gradually applied stricter regulations on the maximum sulphur content permitted in marine fuels and from January 1, 2020, the global fuel sulphur limit was reduced from 3.5% to 0.5%. An attractive option for shipowners is to install exhaust gas cleaning systems, also known as scrubbers, and continue to use high sulphur fuel oil. In the scrubber, the exhausts are led through a fine spray of water, in which sulphur oxides are easily dissolved. The process results in large volumes of acidic discharge water, but while regulations are focused on sulphur oxides removal and acidification, other pollutants e.g. polycyclic aromatic hydrocarbons, metals and nitrogen oxides can be transferred from the exhausts to the washwater and discharged to the marine environment. The aim of the current study was to investigate how different treatments of scrubber discharge water (1, 3 and 10%) affect a natural Baltic Sea summer microplanktonic community. To resolve potential contribution of acidification from the total effect of the scrubber discharge water, "pH controls" were included where the pH of natural sea water was reduced to match the scrubber treatments. Biological effects (e.g. microplankton species composition, biovolume and primary productivity) and chemical parameters (e.g. pH and alkalinity) were monitored and analysed during 14 days of exposure. Significant effects were observed in the 3% scrubber treatment, with more than 20% increase in total biovolume of microplankton compared to the control group, and an even greater effect in the 10% scrubber treatment. Group-specific impacts were recorded where diatoms, flagellates incertae sedis, chlorophytes and ciliates increased in biovolume with increasing concentrations of scrubber water while no effect was recorded for cyanobacteria. In contrast, these effects was not observed in the "pH controls", a suggestion that other parameters/stressors in the scrubber water were responsible for the observed effects.

Particle- and Gaseous Emissions from an LNG Powered Ship.

Measurements of particle number and mass concentrations and number size distribution of particles from a ship running on liquefied natural gas (LNG) were made on-board a ship with dual-fuel engines installed. Today there is a large interest in LNG as a marine fuel, as a means to comply with sulfur and NOX regulations. Particles were studied in a wide size range together with measurements of other exhaust gases under different engine loads and different mixtures of LNG and marine gas oil. Results from these measurements show that emissions of particles, NOX, and CO2 are considerably lower for LNG compared to present marine fuel oils. Emitted particles were mainly of volatile character and mainly had diameters below 50 nm. Number size distribution for LNG showed a distinct peak at 9-10 nm and a part of a peak at diameter 6 nm and below. Emissions of total hydrocarbons and carbon monoxide are higher for LNG compared to present marine fuel oils, which points to the importance of considering the methane slip from combustion of LNG.

Influence of ozone and radical chemistry on limonene organic aerosol production and thermal characteristics.

Limonene has a strong tendency to form secondary organic aerosol (SOA) in the atmosphere and in indoor environments. Initial oxidation occurs mainly via ozone or OH radical chemistry. We studied the effect of O(3) concentrations with or without a OH radical scavenger (2-butanol) on the SOA mass and thermal characteristics using the Gothenburg Flow Reactor for Oxidation Studies at Low Temperatures and a volatility tandem differential mobility analyzer. The SOA mass using 15 ppb limonene was strongly dependent on O(3) concentrations and the presence of a scavenger. The SOA volatility in the presence of a scavenger decreased with increasing levels of O(3), whereas without a scavenger, there was no significant change. A chemical kinetic model was developed to simulate the observations using vapor pressure estimates for compounds that potentially contributed to SOA. The model showed that the product distribution was affected by changes in both OH and ozone concentrations, which partly explained the observed changes in volatility, but was strongly dependent on accurate vapor pressure estimation methods. The model-experiment comparison indicated a need to consider organic peroxides as important SOA constituents. The experimental findings could be explained by secondary condensed-phase ozone chemistry, which competes with OH radicals for the oxidation of primary unsaturated products.

Aging of biogenic secondary organic aerosol via gas-phase OH radical reactions.

The Multiple Chamber Aerosol Chemical Aging Study (MUCHACHAS) tested the hypothesis that hydroxyl radical (OH) aging significantly increases the concentration of first-generation biogenic secondary organic aerosol (SOA). OH is the dominant atmospheric oxidant, and MUCHACHAS employed environmental chambers of very different designs, using multiple OH sources to explore a range of chemical conditions and potential sources of systematic error. We isolated the effect of OH aging, confirming our hypothesis while observing corresponding changes in SOA properties. The mass increases are consistent with an existing gap between global SOA sources and those predicted in models, and can be described by a mechanism suitable for implementation in those models.

Thermal characterization of aminium nitrate nanoparticles.

Amines are widely used and originate from both anthropogenic and natural sources. Recently, there is, in addition, a raised concern about emissions of small amines formed as degradation products of the more complex amines used in CO(2) capture and storage systems. Amines are bases and can readily contribute to aerosol mass and number concentration via acid-base reactions but are also subject to gas phase oxidation forming secondary organic aerosols. To provide more insight into the atmospheric fate of the amines, this paper addresses the volatility properties of aminium nitrates suggested to be produced in the atmosphere from acid-base reactions of amines with nitric acid. The enthalpy of vaporization has been determined for the aminium nitrates of mono-, di-, trimethylamine, ethylamine, and monoethanolamine. The enthalpy of vaporization was determined from volatility measurements of laboratory generated aerosol nanoparticles using a volatility tandem differential mobility analyzer set up. The determined enthalpy of vaporization for aminium nitrates range from 54 up to 74 kJ mol(-1), and the calculated vapor pressures at 298 K are around 10(-4) Pa. These values indicate that aminium nitrates can take part in gas-to-particle partitioning at ambient conditions and have the potential to nucleate under high NO(x) conditions, e.g., in combustion plumes.

Aerosol volatility and enthalpy of sublimation of carboxylic acids.

The enthalpy of sublimation has been determined for nine carboxylic acids, two cyclic (pinonic and pinic acid) and seven straight-chain dicarboxylic acids (C(4) to C(10)). The enthalpy of sublimation was determined from volatility measurements of nano aerosol particles using a volatility tandem differential mobility analyzer (VTDMA) set-up. Compared to the previous use of a VTDMA, this novel method gives enthalpy of sublimation determined over an extended temperature range (DeltaT approximately 40 K). The determined enthalpy of sublimation for the straight-chain dicarboxylic acids ranged from 96 to 161 kJ mol(-1), and the calculated vapor pressures at 298 K are in the range of 10(-6)-10(-3) Pa. These values indicate that dicarboxylic acids can take part in gas-to-particle partitioning at ambient conditions and may contribute to atmospheric nucleation, even though homogeneous nucleation is unlikely. To obtain consistent results, some experimental complications in producing nanosized crystalline aerosol particles were addressed. It was demonstrated that pinonic acid "used as received" needed a further purification step before being suspended as a nanoparticle aerosol. Furthermore, it was noted from distinct differences in thermal properties that aerosols generated from pimelic acid solutions gave two types of particles. These two types were attributed to crystalline and amorphous configurations, and based on measured thermal properties, the enthalpy of vaporization was 127 kJ mol(-1) and that of sublimation was 161 kJ mol(-1). This paper describes a new method that is complementary to other similar methods and provides an extension of existing experimental data on physical properties of atmospherically relevant compounds.