Ship emissions of SO2 and NO2: DOAS measurements from airborne platforms

A unique methodology to measure gas fluxes of SO2 and NO2 from ships using optical remote sensing is described and demonstrated in a feasibility study. The measurement system is based on Differential Optical Absorption Spectroscopy using reflected skylight from the water surface as light source. A grating spectrometer records spectra around 311 nm and 440 nm, respectively, with the telescope pointed downward at a 30A degrees angle from the horizon. The mass column values of SO2 and NO2 are retrieved from each spectrum and integrated across the plume. A simple geometric approximation is used to calculate the optical path. To obtain the total emission in kg h(-1) the resulting total mass across the plume is multiplied with the apparent wind, i.e. a dilution factor corresponding to the vector between the wind and the ship speed. The system was tested in two feasibility studies in the Baltic Sea and Kattegat, from a CASA-212 airplane in 2008 and in the North Sea outside Rotterdam from a Dauphin helicopter in an EU campaign in 2009. In the Baltic Sea the average SO2 emission out of 22 ships was (54 +/- 13) kg h(-1), and the average NO2 emission was (33 +/- 8) kg h(-1), out of 13 ships. In the North Sea the average SO2 emission out of 21 ships was (42 +/- 11) kg h(-1), NO2 was not measured here. The detection limit of the system made it possible to detect SO2 in the ship plumes in 60% of the measurements when the described method was used. A comparison exercise was carried out by conducting airborne optical measurements on a passenger ferry in parallel with onboard measurements. The comparison shows agreement of (-30 +/- 14)% and (-41 +/- 11)%, respectively, for two days, with equal measurement precision of about 20%. This gives an idea of the measurement uncertainty caused by errors in the simple geometric approximation for the optical light path neglecting scattering of the light in ocean waves and direct and multiple scattering in the exhaust plume under various conditions. A tentative error budget indicates uncertainties within 30-45% but for a reliable error analysis the optical light path needs to be modelled. A ship emission model, FMI-STEAM, has been compared to the optical measurements showing an 18% overestimation and a correlation coefficient (R-2) of 0.6. It is shown that a combination of the optical method with modelled power consumption can estimate the sulphur fuel content within 40%, which would be sufficient to detect the difference between ships running at 1% and at 0.1%, limits applicable within the IMO regulated areas

Ammonia and methane emissions from dairy concentrated animal feeding operations in California, using mobile optical remote sensing

Dairy concentrated animal feeding operations (CAFOs) are significant sources of methane (CH4) and ammonia (NH3) emissions in the San Joaquin Valley, California. Optical techniques, namely, remote sensing by Solar Occultation Flux (SOF) and Mobile extractive FTIR (MeFTIR), were used to measure NH3 air column and ground air concentrations of NH3 and CH4, respectively. Campaigns were performed in May and October 2019 and covered 14 dairies located near Bakersfield and Tulare, California. NH3 and CH4 emission rates from single CAFOs averaged 101.9 \ub1 40.6 kgNH3/h and 437.7 \ub1 202.0 kgCH4/h, respectively, corresponding to emission factors (EFs) per livestock unit of 9.1 \ub1 2.7 gNH3/LU/h and 40.1 \ub1 17.8 gCH4/LU/h. The NH3 emissions had a median standard uncertainty of 17% and an expanded uncertainty (95% Confidence Interval (CI)) of 37%; meanwhile, CH4 emissions estimates had greater uncertainty, median of 25% and 53% (in the 95% CI). Decreasing NH3 to CH4 ratios and NH3 EFs from early afternoon (13:00) to early night (19:00) indicated a diurnal emission pattern with lower ammonia emissions during the night. On average, measured NH3 emissions were 28% higher when compared to daytime emission rates reported in the National Emissions Inventory (NEI) and modeled according to diurnal variation. Measured CH4 emissions were 60% higher than the rates reported in the California Air Resources Board (CARB) inventory. However, comparison with airborne measurements showed similar emission rates. This study demonstrates new air measurement methods, which can be used to quantify emissions over large areas with high spatial resolution and in a relatively short time period. These techniques bridge the gap between satellites and individual CAFOs measurements

Measurements of industrial emissions of alkenes in Texas using the solar occultation flux method

Solar occultation flux (SOF) measurements of alkenes have been conducted to identify and quantify the largest emission sources in the vicinity of Houston and in SE Texas during September 2006 as part of the TexAQS 2006 campaign. The measurements have been compared to emission inventories and have been conducted in parallel with airborne plume studies. The SOF measurements show that the hourly gas emissions from the large petrochemical and refining complexes in the Houston Ship Channel area and Mount Belvieu during September 2006 corresponded to 1250 +/- 180 kg/h of ethene and 2140 +/- 520 kg/h of propene, with an estimated uncertainty of about 35%. This can be compared to the 2006 emission inventory value for ethene and propene of 145 +/- 4 and 181 +/- 42 kg/h, respectively. On average, for all measurements during the campaign, the discrepancy factor is 10.2(+ 8,-5) for ethene and 11.7(+ 7,-4) for propene. The largest emission source was Mount Belvieu, NE of the Houston Ship Channel, with ethene and propene emissions corresponding to 440 +/- 130 kg/h and 490 +/- 190 kg/h, respectively. Large variability of propene was observed from several petrochemical industries, for which the largest reported emission sources are flares. The SOF alkene emissions agree within 50% with emissions derived from airborne measurements at three different sites. The airborne measurements also provide support to the SOF error budget

Emission measurements of alkenes, alkanes, SO2, and NO2 from stationary sources in Southeast Texas over a 5 year period using SOF and mobile DOAS

A mobile platform for flux measurements of VOCs (alkanes and alkenes), SO2, and NO2 emissions using the Solar Occultation Flux (SOF) method and mobile differential optical absorption spectroscopy (DOAS) was used in four different studies to measure industrial emissions. The studies were carried out in several large conglomerates of oil refineries and petrochemical industries in Southeast and East Texas in 2006, 2009, 2011, and 2012. The measured alkane emissions from the Houston Ship Channel (HSC) have been fairly stable between 2006 and 2011, averaging about 11,500kg/h, while the alkene emissions have shown greater variations. The ethene and propene emissions measured from the HSC were 1511kg/h and 878kg/h, respectively, in 2006, while dropping to roughly 600kg/h for both species in 2009 and 2011. The results were compared to annual inventory emissions, showing that measured VOC emissions were typically 5-15 times higher, while for SO2 and NO2 the ratio was typically 0.5-2. AP-42 emission factors were used to estimate meteorological effects on alkane emissions from tanks, showing that these emissions may have been up to 35-45% higher during the studies than the annual average. A more focused study of alkene emissions from a petrochemical complex in Longview in 2012 identified two upset episodes, and the elevation of the total emissions during the measurement period due to the upsets was estimated to be approximately 20%. Both meteorological and upset effects were small compared to the factor of 5-15, suggesting that VOC emissions are systematically and substantially underestimated in current emission inventories

Interactions between dietary patterns and genetic factors in relation to incident dementia among 70-year-olds

PURPOSE: To investigate potential interactions between dietary patterns and genetic factors modulating risk for Alzheimer's disease (AD) in relation to incident dementia. METHODS: Data were derived from the population-based Gothenburg H70 Birth Cohort Studies in Sweden, including 602 dementia-free 70-year-olds (examined 1992-93, or 2000-02; 64% women) followed for incident dementia until 2016. Two factors from a reduced rank regression analysis were translated into dietary patterns, one healthy (e.g., vegetables, fruit, and fish) and one western (e.g., red meat, refined cereals, and full-fat dairy products). Genetic risk was determined by APOE ε4 status and non-APOE AD-polygenic risk scores (AD-PRSs). Gene-diet interactions in relation to incident dementia were analysed with Cox regression models. The interaction p value threshold was < 0.1. RESULTS: There were interactions between the dietary patterns and APOE ε4 status in relation to incident dementia (interaction p value threshold of < 0.1), while no evidence of interactions were found between the dietary patterns and the AD-PRSs. Those with higher adherence to a healthy dietary pattern had a reduced risk of dementia among ε4 non-carriers (HR: 0.77; 95% CI: 0.61; 0.98), but not among ε4 carriers (HR: 0.86; CI: 0.63; 1.18). Those with a higher adherence to the western dietary pattern had an increased risk of dementia among ε4 carriers (HR: 1.37; 95% CI: 1.05; 1.78), while no association was observed among ε4 non-carriers (HR: 0.99; CI: 0.81; 1.21). CONCLUSIONS: The results of this study suggest that there is an interplay between dietary patterns and APOE ε4 status in relation to incident dementia

Fixed remote surveillance of fuel sulfur content in ships from fixed sites in the Göteborg ship channel and Öresund bridge

In 2015 new rules from the IMO and legislation from EU (Sulfur directive) and the US requires ships to run with maximum fuel sulfur content (FSC) of 0.1 % m/m in northern European and North American waters. In order to promote a level playing field within the shipping sector, there is a need for measurement systems that can make effective compliance control and this is the main objective of the CompMon project, funded through the European CEF program (Connecting Europe Facility). As part of this project, an automatic sniffer sensor system has been applied in the Göteborg ship channel at the Älvsborg island during 3 years (2014- 2016) and at the Öresund Bridge during two months at the end of 2016. The typical distances from the ships here varied between 500 -1000 m. The sniffer system is based on several extractive instruments measuring concentrations of SO2 and CO2 and others species, such as NOx, in the ship emission plumes that drift over the measurement station. In addition to fixed stations, the system can also be used from mobile platforms such as harbor patrol vessels and aircraft. From the data above, together with information about the ships from AIS (Automatic Identification System) and wind data, the FSC is automatically calculated and the ship is identi- fied. This is done using software developed as part of this project (Single Emitter identification Tool).The measurement precision (1σ) of the sniffer system is approx. 0.04 % m/m for ships using a FSC of 0.1 % m/m. The sniffer system also has a negative bias in the measured FSC, varying between 0.04 % to 0.08 % m/m and this is accounted for when calculating the threshold for non-compliance. Based on the above, it is possible to identify ships with FSC above 0.18 % m/m with 95% confidence limit, if the bias is corrected for statistically. For the measurements at the Älvsborg island site in 2014 and 2015, the corresponding limit is higher, 0.29 % m/m, due to a measurement artifact that was eliminated in 2016. On board measurements in 2015 and 2016 by the Swedish port state control authority shows that most non-compliant ships had FSCs be- tween 0.1 % to 0.2 % m/m when controlled at berth and this is generally below the 95% confidence limit threshold of the sniffer. Therefore many non-compliant ships will not be detected when using the sniffer close to harbors and a more precise sensor is therefore preferred.The measurements at the Älvsborg island were carried out during a time period when the allowed FSC limit changed significantly. The data for 2014, corresponding to more than 4000 measurements of 500 individual ships, shows that 99 % of the ships were using compliant fuel below the FSC limit of 1 % m/m. In 2015 the FSC limit changed to 0.1 % m/m. The measurements in 2015 and 2016, corresponding to the same amount of ships as in 2014, showed that 91.5 % and 98 %, respectively, were using compliant fuel with respect to FSC. The lower compliance rate in 2015 compared to 2016 is potentially influenced by measurement artifacts that were later eliminated in 2016. At the Öresund Bridge. 58 ships were measured as part of the CompMon pro- ject. The measurements continued another month with support from the interreg project Envisum, with anoth- er 62 ships measured. The compliance level at the Öresund Bridge corresponds to 98 %. This is actually com- parable to the corresponding measurements elsewhere and at the Älvsborg island site during the same time period

A new method to detect long term trends of methane (CH₄) and nitrous oxide (N₂O) total columns measured within the NDACC ground-based high resolution solar FTIR network

Total columns measured with the ground-based solar FTIR technique are highly variable in time due to atmospheric chemistry and dynamics in the atmosphere above the measurement station. In this paper, a multiple regression model with anomalies of air pressure, total columns of hydrogen fluoride (HF) and carbon monoxide (CO) and tropopause height are used to reduce the variability in the methane (CH4) and nitrous oxide (N2O) total columns to estimate reliable linear trends with as small uncertainties as possible. The method is developed at the Harestua station (60°N, 11°E, 600ma.s.l.) and used on three other European FTIR stations, i.e. Jungfraujoch (47°N, 8°E, 3600ma.s.l.), Zugspitze (47°N, 11°E, 3000ma.s.l.), and Kiruna (68°N, 20°E, 400ma.s.l.). Linear CH4 trends between 0.13±0.01-0.25±0.02%yr−1 were estimated for all stations in the 1996-2009 period. A piecewise model with three separate linear trends, connected at change points, was used to estimate the short term fluctuations in the CH4 total columns. This model shows a growth in 1996–1999 followed by a period of steady state until 2007. From 2007 until 2009 the atmospheric CH4 amount increases between 0.57±0.22–1.15±0.17%yr−1. Linear N2O trends between 0.19±0.01–0.40±0.02%yr−1 were estimated for all stations in the 1996-2007 period, here with the strongest trend at Harestua and Kiruna and the lowest at the Alp stations. From the N2O total columns crude tropospheric and stratospheric partial columns were derived, indicating that the observed difference in the N2O trends between the FTIR sites is of stratospheric origin. This agrees well with the N2O measurements by the SMR instrument onboard the Odin satellite showing the highest trends at Harestua, 0.98±0.28%yr−1, and considerably smaller trends at lower latitudes, 0.27±0.25%yr−1. The multiple regression model was compared with two other trend methods, the ordinary linear regression and a Bootstrap algorithm. The multiple regression model estimated CH4 and N2O trends that differed up to 31% compared to the other two methods and had uncertainties that were up to 300% lower. Since the multiple regression method were carefully validated this stresses the importance to account for variability in the total columns when estimating trend from solar FTIR data

Surveillance of Sulfur Emissions from Ships in Danish Waters

In 2015 new rules from the IMO and legislation from EU (Sulfur directive) requires ships to run with maximum fuel sulfur content (FSC) of 0.1 % m/m in northern European waters. In order to promote a level playing field within the shipping sector, there is a need for measurement systems that can make effective compliance control. This report describes the results from ship emission measurements on the waters surrounding Denmark from June 2015 to July 2017 on behalf of the Danish Environmental Protection Agency. The overall aim was to carry out operational surveillance of ships with respect to the EU sulfur directive and particularly the sulfur limits for marine fuel in the European Sulfur Emission Control Area (0.10 %), which entered into force on January 1st 2015, as well as to guide further port state control of ships at the destination harbors of the ships, both in Denmark and other ports. During the project the FSC of individual ships was estimated by perform- ing spot checks of exhaust plumes of individual ships. This was conducted by automatic gas sniffer measurements at the Great Belt Bridge and airborne surveillance measurements using sniffer and optical sensors. The data from the fixed system were transmitted in real time to a web database and alarms were triggered for high FSC ships in the form of emails. The report describes the technical systems and their performance and the general compliance levels of the measured ships. The measurement systems have been developed by Chalmers University of Technology through Swedish national funding and the EU project CompMon. The airborne dataset corresponds to approx. 900 individual ships, measured by sniffer or/and optical sensor over 245 flight hours. The optical sensor has low precision and is therefore used as a first alert system to identify ships running on high sulfur fuel. The precision of the airborne FSC meas- urements by the sniffer system is better and it is estimated as \ub1 0.05 % m/m (1σ) with a systematic bias of - 0.045 % m/m. Therefore only ships running with FSC of 0.2 % m/m or higher can be de- tected as non-compliant ships with good confidence limit (95 %) by the airborne sniffer system. The airborne measurements during 2015 and 2016 on Danish waters show that 94 % of the ships complied with the EU Sulphur directive, at the 95 % confidence limit. The compliance rate was lower, 92 %, during the 2nd half of 2016. In the period June 2015 to May 2017, 8426 sniffer measurements of individual ships were carried out at the Great Belt Bridge. However, there were technical problems in the first part of the project and the sniffer therefore had reduced sensitivity the first year and only high sulfur ships (&gt; 1 % FSC) could be detected as non-complying vessels with appropriate statistical confidence. The precision in the estimated FSC by the fixed sniffer system is estimated as \ub1 0.04 % m/m (1σ) with a systematic bias of - 0.055 % m/m. Therefore only ships running with FSC of 0.18 % or higher can be detected as non-compliant ships with good confidence limit (95 %) by the fixed sniffer system. The data for the period June 2016 to October 2016 show a compliance rate of 94.6 % which increased to 97.4 % in the period January 2017 to May 2017. The compliance level during different time periods and platforms varied between 92-97 %. Here 1 - 2 % of the ships were in gross non-compliance with the EU sulfur directive with FSC values above 0.5 % m/m. There were differences over time, with the highest values in the summer of 2016. The compliance level was close to the values (95 %) measured by port state control authorities in Sweden and Denmark 2015 and 2016. When comparing ships measured by port state and the ones in this project it can be deduced that the efficiency of finding non-compliant vessels could be increased by at least a factor of 4, if the port state controls were guided by measurements. Most of the non-compliant ships (90 %) were measured high only once. But there were cases with individual ships and ship operators that were more abundant in the non-compliance statistics. The non- compliant ships that were seldom in the area around Denmark had higher emissions of SO2 than the non-compliant ones that operated their more frequently. On several occasions during this study we encountered ships equipped with scrubbers that were non-compliant with respect to the EU sulfur directive

Certification of an aircraft and airborne surveillance of fuel sulfur content in ships at the SECA border

In 2015 new rules from the IMO and legislation from EU (Sulfur directive) and the US requires ships to run with maximum fuel sulfur content (FSC) of 0.1 % m/m in northern European and North American waters. In order to promote a level playing field within the shipping sector, there is a need for measurement systems that can make effective compliance control and this is the main objective of the CompMon project, funded through the European CEF program (Connecting Europe Facility). As part of this project, a sensor system has been certified for ship surveillance measurements in a Piper Navajo aircraft and it has been demonstrated for airborne measurements of FSC in individual ships on the English Channel. The measurement system consists of an optical module which measures total emissions of SO2 and NO2 in g/s and a sniffer system by which FSC is retrieved from extractive measurements of SO2 and CO2. It can be used from fixed sites, patrol vessels and from aircraft. The advantage with airborne surveillance is the capability to check ships that are operating in the main shipping lanes, up to 200 nautical miles from shore. The precision of the estimated FSC from the sniffer system is 0.05 % m/m and hence at the 95 % confidence limit, ships above a FSC of 0.2 % m/m can be checked. The sniffer system also has a negative bias in the FSC of approx- imately 0.04 % m/m which is accounted for in the FSC calculations. The optical system has larger measurement uncertainties than the sniffer but it is intended mostly for guid- ance of other controls. As part of the CompMon project, a measurements campaign with the Navajo Piper aircraft was carried out at the SECA (Sulfur Emission Control Area) border in the English Channel at longitude 5 W. Six flight missions with duration of 4 to 5 hours were carried out from September 2 to 10, 2016, flying from Brest airport. In this manner it was possible to cover the longitude range 2o - 6o W. During the campaign, 114 ships were measured with the sniffer system, corresponding to 71 ships inside the SECA and 42 ships outside. The level of compli- ance inside the SECA was here 87 % and this is considerably lower than measurements carried out elsewhere within CompMon in other parts of the SECA (95-99 %). Two thirds of the non-complying vessels were leav- ing the SECA. With the optical system 110 individual ships were measured, 42 outside and 68 inside the SE- CA. The measurements show a similar pattern as the sniffer data but with a few false values. Nevertheless it is shown that both low and high FSC ships will be classified correctly with about 80-90 % probability with the optical system and this system is hence very promising as a tool to guide further compliance controls

Passive and active suicidal ideation in a population-based sample of older adults: Associations with polygenic risk scores of relevance for suicidal behavior

Introduction: There are few studies investigating genetic factors related to suicidal ideation or behavior in older adult populations. Our aim was to test associations between passive and active suicidal ideation and polygenic risk scores (PRSs) for suicidality and other traits of relevance for suicidality in old age (i.e. depression, neuroticism, loneliness, Alzheimer’s disease, cognitive performance, educational attainment, and several specified vascular diseases) in a population-based sample aged 70 years and older. / Methods: Participants in the prospective H70 study in Gothenburg, Sweden, took part in a psychiatric examination that included the Paykel questions on active and passive suicidal ideation. Genotyping was performed with the Neurochip (Illumina). After quality control of the genetic data the sample included 3467 participants. PRSs for suicidality and other related traits were calculated based on summary statistics from recent GWASs of relevance. Exclusion of persons with dementia or incomplete data on suicidal ideation yielded 3019 participants, age range 70–101 years. Associations between past year suicidal ideation (any level) and selected PRSs were analysed using general estimation equation (GEE) models, adjusted for sex and age. / Results: We observed associations between passive/active suicidal ideation and PRSs for depression (three versions), neuroticism, and general cognitive performance. After excluding individuals with current major depressive disorder (MDD), similar associations were seen with PRS for neuroticism, general cognitive performance and two PRSs for depression. No associations were found between suicidal ideation and PRSs for suicidality, loneliness, Alzheimer’s disease, educational attainment, or vascular disease. / Discussion: Our results could indicate which types of genetic susceptibility that are of importance for suicidality in old age, and these findings can help to shed light on potential mechanisms that may be involved in passive and active suicidal ideation in late-life, also in those with no current MDD. However, due to the limited sample size, the results need to be interpreted with caution until replicated in larger samples