Sulfur Regulation Research Articles

Impact of fuel sulfur regulations on carbonaceous particle emission from a marine engine

Ship traffic substantially contributes to air pollution, thus affecting climate and human health. Recently introduced regulations by the International Maritime Organization (IMO) on the fuel sulfur content (FSC) caused a shift in marine fuel onsumption from heavy fuel oils (HFO) to diesel-like distillate fuels, but also to alternative hybrid fuels and the operation of sulfur scrubbers. Using multi-wavelength thermal-optical carbon analysis (MW-TOCA), our study provides emission factors (EF) of carbonaceous aerosol particles and link the fuel composition to features observed in the soot microstructure, which may be exploited in online monitoring by single-particle mass spectrometry (SPMS). Particulate matter from distillate fuels absorbs stronger light of the visible UV and near-infrared range than HFO. However, Simple Forcing Efficiency (SFE) of absorption weighted by EF of total carbon compensated the effect, leading to a net reduction by >50% when changing form HFO to distillate fuels.

Simultaneous regulation of nitrogen, sulfur and carbon using biochar during sewage sludge pyrolysis

Due to the complex nature of sewage sludge (SS), how to control the emission of precursor pollutants during its pyrolysis remains a challenge. In this work, the evolution of N, S and C during SS pyrolysis was investigated and biochars were employed to regulate their distribution in the resulting products. The release of N-containing products followed a descending order of NH3>HCN > NO > NO2 and the biochar addition resulted in a reduction of 40.7–54.3 % for these volatiles. The nitrile-N and pyrrolic-N species decreased, while the quaternary-N in residue increased significantly. The emission of S-containing products showed a descending order of COS > SO2>CH3SH > H2S > CS2 and the co-pyrolysis with biochar showed a reduction of 40.6–65.7 % for these products. The relative contents of thiophene-S and sulfoxide-S species increased, while the content of sulfone-S decreased. Biochar incorporation also resulted in a reduction of 67.2 % and 47.4 % for CO and CO2, respectively. Both Raman and XPS analysis indicated an increase in the graphitization degree and a decrease in structural defects.

Магнетит как функциональный наполнитель эластомерных композитов: эффекты размерности и структурирования

Samples of composite materials based on Fe3O4 magnetite with different particle sizes (natural and crushed in a planetary mill) and various elastomeric matrices (chloroprene rubber of sulfur regulation – PCP, styrene butadiene rubber - BSK and cold-cured polydimethylsiloxane – SKTN-A) in the concentration range of 10...200 weight parts per 100 weight parts of elastomeric matrices. The kinetics of curing of the elastomeric compositions under consideration has been studied, on the basis of which optimal molding modes have been proposed. The samples were formed both in the presence of a magnetic field up to 0.3 T and without it. The functional (electrophysical and magnetic) properties of the samples were studied and it was shown that these properties in a wide range of values can be regulated by changing the size of magnetite particles and/or structuring them by means of a magnetic field during the molding of elastomeric composites.

Enhancement of nitrogen removal in constructed wetlands through boron mud and elemental sulfur addition: Regulation of sulfur and oxygen cycling

Constructed wetlands (CWs) utilizing elemental sulfur (S0) as an electron donor are effective for nitrate (NO3–-N) removal from low C/N wastewater. However, the limited bioavailability of chemical S0 (chem-S0) due to low water solubility and inadequate mass transfer impedes complete denitrification. In this study, boron mud waste and S0 (S0&BM) were processed and combined to convert chem-S0 to biological S0 (bio-S0) in CWs. The employment of S0&BM improved NO3–-N and total nitrogen (TN) removal rates by 15.36 % and 10.55 % compared to S0 alone. The 15N isotope tracing experiment unveiled the pathways of N2O production and demonstrated that S0&BM facilitated full denitrification, resulting in a higher percentage of nitrogen being degraded in a non-polluting form (54.70 %). Releasing trace amounts of boron and magnesium in S0&BM mitigated the excessive acidification caused by the sulfur autotrophic process and promoted biofilm formation, thereby pronouncing vertical oxygen fluctuations. Meanwhile, oxygen vacancies generated in the S0&BM promoted the closed-loop sulfur cycle, starting from the oxidation of chem-S0 to sulfate (SO42-), the important process of SO42--reducing bacteria using partial organic compounds as electron donors to reduce SO42- to sulfide (S2-) was realized, and finally the S2- was oxidized to bio-S0 with better properties. S0&BM enriched functional microbial communities in the biofilm related to nitrogen and sulfur transformation. Functional gene analysis showed an increase in the narG, nirS, norB, and nosZ genes supporting denitrification. The dsrA and sqr genes responsible for the sulfur cycle exhibited the highest abundance. This realization allowed for the utilization of waste materials for treatment, enhancing the energy efficiency of carbon reduction and pollution reduction in CWs.

Effect of the low sulphur regulations of maritime fuels on ambient air quality: a case study in the Bosphorus strait

Effect of the low sulphur regulations of maritime fuels on ambient air quality: a case study in the Bosphorus strait

Measurement report: Vanadium-containing ship exhaust particles detected in and above the marine boundary layer in the remote atmosphere

Abstract. Each year, commercial ships emit over 1.67 Tg of particulate matter (PM) pollution into the atmosphere. These ships rely on the combustion of heavy fuel oil, which contains high levels of sulfur, large aromatic organic compounds, and metals. Vanadium is one of the metals most commonly associated with heavy fuel oil and is often used as a tracer for PM from ship exhaust. Previous studies have suggested that vanadium-containing PM has impacts on human health and climate due to its toxicological and cloud-formation properties, respectively; however, its distribution in the atmosphere is not fully understood, which limits our ability to quantify the environmental implications of PM emitted by ships. Here, we present data obtained from a Particle Analysis by Laser Mass Spectrometry (PALMS) instrument on the NASA DC-8 aircraft during the 2016–2018 Atmospheric Tomography Mission (ATom) and show that ∼ 1 % of the accumulation mode particles measured in the marine boundary layer of the central Pacific and Atlantic oceans contain vanadium. These measurements, which were made without targeting ship plumes, suggest that PM emitted by ships is widespread in the atmosphere. Furthermore, we observed vanadium-containing ship exhaust particles at altitudes up to 13 km, which demonstrates that not all ship exhaust particles are immediately removed via wet deposition processes. In addition, using laboratory calibrations, we determined that most vanadium-containing ship exhaust particles can contain up to a few weight percent of vanadium. This study furthers our understanding of both the chemical composition and distribution of PM emitted by ships, which will allow us to better constrain the climate, health, and air quality implications of these particle types in the future. We note that these data were collected prior to the 2020 International Maritime Organization (IMO) sulfur regulation and stand as a reference for understanding how ship emissions have evolved in light of these regulations.

Difference in sulfur regulation mechanism between tube-dwelling and free-moving polychaetes sympatrically inhabiting deep-sea hydrothermal chimneys

The environment around deep sea hydrothermal vents is characterized by an abundance of sulfur compounds, including toxic hydrogen sulfide. However, numerous communities of various invertebrates are found in it. It is suggested that invertebrates in the vicinity of hydrothermal vents detoxify sulfur compounds by biosynthesis of taurine-related compounds in the body. On the other hand, the vent endemic polychaete Alvinella pompejana has spherocrystals composed of sulfur and other metals in its digestive tract. It was considered that the spherocrystals contribute to the regulation of sulfur in body fluids. Paralvinella spp. and Polynoidae. gen. sp. live sympatrically and in areas most affected by vent fluid. In this study, we focused on the digestive tract of Paralvinella spp. and Polynoidae. gen. sp. to examine whether they have spherocrystals. We also investigated the possible involvement of bacteria in the digestive tract in spherulization. Examination with a scanning electron microscope (SEM) equipped with Energy Disperse X-ray Spectroscopy (EDS) detected spherocrystals containing sulfur and iron in the digestive tract of Paralvinella spp. In contrast, such spherocrystals were not observed in that of Polynoidae. gen. sp. although sulfur is detected there by inductively coupled plasma-optical emission spectrometry (ICP-OES). Meta-16S rRNA analysis indicated that the floras of the digestive tracts of the two species were very similar, suggesting that enteric bacteria are not responsible for spherocrystal formation. Analysis of taurine-related compounds indicated that the digestive tissues of Polynoidae. gen. sp. contain a higher amount of hypotaurine and thiotaurine than those of Paralvinella spp. Therefore, the two sympatric polychaetes use different strategies for controlling sulfur, i.e., Paralvinella spp. forms spherocrystals containing elemental sulfur and iron in the digestive tract, but Polynoidae. gen. sp. accumulates taurine-related compounds instead of spherocrystals. Such differences may be related to differences in their lifestyles, i.e., burrow-dweller or free-moving, or may have been acquired phylogenetically in the evolutionary process.

Detection of large-scale cloud microphysical changes within a major shipping corridor after implementation of the International Maritime Organization 2020 fuel sulfur regulations

Abstract. New regulations from the International Maritime Organization (IMO) limiting sulfur emissions from the shipping industry are expected to have large benefits in terms of public health but may come with an undesired side effect: acceleration of global warming as the climate-cooling effects of ship pollution on marine clouds are diminished. Previous work has found a substantial decrease in the detection of ship tracks in clouds after the IMO 2020 regulations went into effect, but changes in large-scale cloud properties have been more equivocal. Using a statistical technique that estimates counterfactual fields of what large-scale cloud and radiative properties within an isolated shipping corridor in the southeastern Atlantic would have been in the absence of shipping, we confidently detect a reduction in the magnitude of cloud droplet effective radius decreases within the shipping corridor and find evidence for a reduction in the magnitude of cloud brightening as well. The instantaneous radiative forcing due to aerosol–cloud interactions from the IMO 2020 regulations is estimated as O(1 W m−2) within the shipping corridor, lending credence to global estimates of O(0.1 W m−2). In addition to their geophysical significance, our results also provide independent evidence for general compliance with the IMO 2020 regulations.

Phosphorus and sulfur regulation of ferrum doped carbon nitride for efficient photocatalytic PPCPs degradation under visible-light irradiation

In this study, a novel Fe, S, P co-doped g-C3N4 photocatalytic nanoreactor was successfully synthesized. The unique structure of Fe, S, P co-doped g-C3N4 enhances its optical absorption, and there are plenty of active sites and photogenerated carrier separation. Consequently, the Fe, S, P co-doped g-C3N4 demonstrated excellent photocatalytic-Fenton degradation activities under visible light irradiation. Remarkedly, 5 mg/L of sulfamethazine (SMZ) is completely photocatalytic-Fenton degraded following 25 min under visible light irradiation. It further shows that·O2- plays a crucial part in the photocatalytic-Fenton process, leading to the decomposition of sulfamethazine. The decline of Bisphenol A (BPA) further demonstrates that this photocatalytic-Fenton system can be effectively used to remediate pharmaceutical and personal care product contamination in environmental waterways.

A risk assessment of scrubber use for marine transport by rule-based fuzzy FMEA

To comply with the International Maritime Organization’s sulfur regulations, shipping companies have mainly favored scrubber systems. Even though the ship’s operations might be continued provided regulatory constraints are followed, the installation presents system-based risks depending on the scrubber type. This study’s primary aim is to inform the shipping industry about the risks associated with various scrubber applications on ships and to propose guidelines to ensure safer scrubber operation on marine vessels. Consequently, a risk evaluation is conducted on all kinds of scrubber systems. Experts in the marine industry identify the main subsystems and components and evaluate their failure modes and consequences. Using the fuzzy failure modes and effects analysis method, the acquired judgments are analyzed. The risk value of each failure scenario is computed using the Mamdani fuzzy inference technique and the evaluation of expert ratings. The riskiest failure modes identified by the investigation include the sensing element, injection nozzles, packed peds, and seawater system valves.

Optimal compliance choices for ocean carriers under the sulphur regulation

Optimal compliance choices for ocean carriers under the sulphur regulation

Article: Green Shipping and Trade: Allocating Costs of the IMO Sulphur Regulation 2020

In January 2020 the Internatoinal Maritime Organisation (IMO) imposed, down from 3.5% m/m, a new limit of 0.50% m/m Sulphur limit from exhaust gases originating from commercial vessels. This new standard forced the maritime industry to switch to compliant fuels (such as Very Low Sulphur Fuel Oil (VLSFO) and ultra-low sulphur fuel oil (ULSFO) blends) or use an exhaust gas cleaning system (EGCS). Although there may be a consensus that this is a good thing, achievement of benefits has created contractual challenges for the industry. Responsibilities are divided between shipowner and charterer through forming a voyage charter, a time charter, or a bareboat charter (BBC). Baltic and International Maritime Council (BIMCO) and Intertanko provide standard contracts allocating the responsibilities of compliance with IMO Sulphur regulations between shipowner and charterer under the time charter. The compliance obligations under the voyage charterparty and BBC are still unaddressed. Here, we address them and offer an allocation of the responsibility. Charterparty, VLSFO, EGCS, contract, obligation, fixtures, Sulphur

Analysing the environmental impact of IMO sulphur regulation 2020, annex VI, MARPOL

The IMO has set different SOx limits over the years, including different limits for SECA and areas outside SECA. The EU has formulated stricter limits for its member states. The EU port and SECA areas have reduced SOx emissions vastly. Ocean acidification, degradation of the environment, and human health has been improved in the EU ports and SECA areas. However, the improvement at the global level is limited. SOx emission causes a cooling effect on temperature and decreases the warming effect of GHG emissions. The lowering of SOx can impact global warming. Further, the Black Carbon emission from alternate fuels can lead to increased GHG emissions. The acidic wash water from EGCS contains toxic metals and PAHs which when discharged at sea cause severe damage. The SOx reduction, Black Carbon emission and wash water discharge adversely impact oceans and violates the UNCLOS, UNFCCC, Paris Agreement, CBD, and even the UNDRIP. An IPCC report will help analyse the SOx, Black Carbon emission, and wash water impact, which can be taken up in COP 28. The 2022 MEPC Guidelines for Environmental Risk Assessment and reception of wash water, with Port authorities are based on the submissions by nations and environmental organizations to the PPR 9, which have highlighted the environmental problems and challenges in the use of EGCS and the discharge of its wash water. The guidelines are non-binding and may not have the desired impact. Much stricter regulation is required to ensure the protection of the marine environment.

Nitric Oxide- and Sulfur-Mediated Reversal of Cadmium-Inhibited Photosynthetic Performance Involves Hydrogen Sulfide and Regulation of Nitrogen, Sulfur, and Antioxidant Metabolism in Mustard

This study aimed to test the role of hydrogen sulfide (H2S) in the responses regarding the nitric oxide- (NO) and sulfur (S)-mediated improvement in photosynthesis and growth under cadmium (Cd) stress in mustard (Brassica juncea L. cv. Giriraj), and integrate the mechanisms of S, nitrogen (N), and antioxidant metabolism. The plants grown with Cd (200 mg Cd kg−1 soil) exhibited reduced assimilation of S and N and diminished photosynthetic performance, which was associated with higher Cd accumulation-induced excess reactive oxygen species (ROS) production. The application of 100 μM of sodium nitroprusside (SNP, a NO donor) together with a more prominent concentration of S resulted in increased photosynthetic S- and N-use efficiency, production of non-protein thiols and phytochelatins, efficiency of enzymatic (superoxide dismutase, ascorbate peroxidase, and glutathione reductase), non-enzymatic antioxidants (ascorbate and glutathione) limiting Cd accumulation and, thus, reduced oxidative stress (superoxide radical, hydrogen peroxide, and thiobarbituric acid reactive species content). The benefit of NO together with S was manifested through a modulation in H2S production. The use of 100 μM of hypotaurine (HT; H2S scavenger) or 100 μM of cPTIO (2-4-carboxyphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) in plants treated with NO plus S reversed the action of NO plus S, with a higher reduction in photosynthesis and growth with the use of HT, suggesting that H2S plays a significant role in the NO- and S-mediated alleviation of Cd stress. The interplay of NO and ES with H2S may be used in augmenting the photosynthesis and growth of Cd-grown mustard plants.

Impact of IMO Sulfur Regulations on Air Quality in Busan, Republic of Korea

In this study, we investigate the air quality improvement effect in Busan, the largest port city in South Korea, caused by the implementation of International Maritime Organization (IMO) sulfur regulations. Currently, the Korean government is struggling with problems related to PM2.5, and ships are one of the major sources of PM2.5 generation in South Korea. Therefore, we tried to estimate how much the PM2.5 levels in South Korea could be improved via low-sulfur regulation. According to the Clean Air Quality Policy Support System (CAPSS; National Emission Inventory) in 2016, ship emissions in Busan accounted for 39%, 71%, and 39% of PM2.5, SO2, and NO2 emissions, respectively. To simulate the effect of the IMO’s 0.5 percent sulfur regulation, SOx and PM2.5 emissions from oil-fueled cargo ships were reduced. Via ship fuel regulation, the PM2.5 concentration was improved by up to 19% at a site near the port in 2020. In addition, in the case of sulfate, the reduction rate was higher on the downwind side of the Busan port and not near the port, which can be considered as the cause of advection and secondary formation. The PM2.5 contributions from ships to each of the sub-regions in Busan also decreased by an average of 47% because of IMO sulfur regulation. Although there were limitations in terms of emission estimations because of the application of low-sulfur regulation, we expect that the results of this paper can be used for additional PM2.5 improvement plans developed by the Korean government and by the local government as well.

The Reality Gap: Simplification of Environmental Law as Key for the Acceleration of Permit Procedures for Europe’s Green Deal

To reach climate goals, there is a need for large scale changes to the energy system. This requires speedy permitting procedures. However, permitting procedures are everything else but speedy. Thus, there is a need to simplify the rules to accelerate the permit procedures. While permitting procedures are largely governed by national law, the central issue for large scale infrastructure projects is to handle the high standards of EU Environmental law. Enlarged rights of individuals and Non-Governmental Organizations (NGOs) to bring any mistaken application of these rules to court and thus stop projects from realization for years, represent the major risks of delay for the realization of infrastructure projects. Shortcomings on the application of EU Environmental law in permitting procedures are not only caused by narrow time schedules and stingy project promoters, but mainly by an overcomplex system of partly unclear rules that is evolving in the jurisdiction of the European Court of Justice (ECJ) only in one direction: Making every single rule even stricter case by case before the ECJ. This is reality. To cut on the duration of permit procedures for reaching climate goals in time, European environmental law needs to be adapted. Without streamlining and simplifying EU environmental law, all efforts to accelerate permit procedures are doomed to failure. This article suggests adaptations of the European Habitats and Birds Directives, Water Framework Directive and Environmental Impact Assessments Directive to significantly accelerate permit procedures. IMO Sulphur Regulation, Shipowner, Charterer, EGCS, Low Sulphur Fuel

Global reduction in ship-tracks from sulfur regulations for shipping fuel.

Ship-tracks are produced by ship-emitted aerosols interacting with low clouds. Here, we apply deep learning models on satellite data to produce the first global climatology map of ship-tracks. We show that ship-tracks are at the nexus of cloud physics, maritime shipping, and fuel regulation. Our map captures major shipping lanes while missing others because of background conditions. Ship-track frequency is more than 10 times higher than a previous survey, and its interannual fluctuations reflect variations in cross-ocean trade, shipping activity, and fuel regulations. Fuel regulation can alter both detected frequency and shipping routes due to cost. The 2020 fuel regulation, together with the coronavirus disease 2019 pandemic, reduced ship-track frequency to its lowest level in recent decades across the globe and may have ushered in an era of low frequency. The regulation reduces the aerosol indirect forcing from ship emissions by 46% or between 0.02 and 0.27 W m−2 given its current estimates.

Transformation and regulation of nitrogen and sulfur during pyrolysis of oily sludge with N/S model compounds

Pyrolysis of oily sludge (OS) is an alternative for energy recovery with less pollutants. However, the migration of nitrogen and sulfur during pyrolysis process remain challenges for environmental concern and subsequent utilization of the recovered fuel. In this work, stage pyrolysis experiments of polyacrylamide (PAM) and sodium dodecyl sulfonate (SDS) under OS surroundings were conducted in a thermogravimetry-mass spectrometry-infrared spectroscopy and a fixed reactor to investigate the transformation behaviors of N/S-containing pollutants. Ca(OH)2 and Fe2O3 were then used as inhibitors to regulate nitrogen and sulfur behaviors. Results showed that 3,3 dimethylpyrrolidine-2,5-dione (C6H9NO2), glutarimide (C5H7NO2) and NH3 were the primary N-containing pollutants in liquid and gaseous products, which were generated from PAM via deamination reactions at 200–400 °C. SO2 was the dominant S-containing pollutant, which was generated from SDS via desulfonation at temperature below 300 °C. The dosage of Ca(OH)2 catalyzed the deamination and cracking reactions, and thus led to more N/S-containing pollutants. Fe2O3 suppressed the N/S-containing pollutants significantly because it could increase the energy barrier of N/S-containing pollutants and fix the released NH3 and SO2 into solid residues. This work facilitated the understanding of the nitrogen and sulfur transformation behaviors and would provide a possible regulatory strategy for clean fuel recovery.

Role of gas coal in sulfur regulation from the release behavior and mass transfer condition of volatiles

There were new restrictions on sulfur regulation of high organic-sulfur coal (HOSC: A) brought by the differences in the pyrolysis characteristics of different gas coals (GC: B and C) and the mass transfer conditions of their volatiles. Firstly, the role of volatiles from GC in the sulfur regulation along vertical and horizontal directions was revealed by designing two stacking modes in a cylindrical crucible and using the parallel and cylindrical baffles to block the volatiles’ migration. Secondly, the different performances of volatiles from two different GC on the sulfur regulation were associated with their volatiles’ release behaviors. And finally, the effect of mass transfer conditions of volatiles on the sulfur regulation was discussed and reflected in the sulfur spatial distribution in chars. Contrast experiments with or without parallel and cylindrical baffles indicated that the monodirectional migration of volatiles from GC helped reduce the sulfur contents along both vertical and horizontal directions. The maximum distances of effective sulfur removal by volatiles from GC along vertical and horizontal directions varied respectively within 5 ∼ 15 and 8 ∼ 15 mm as changing GC. The performance of different GC in sulfur removal depended on the good match of its intensive volatiles release to the high permeability of HOSC and the continuous supply of hydrogen-rich volatiles. The effective distance of bi-directional vertical migration of volatiles was shortened to 3 ∼ 6 mm. It was promising to use the effective distance of sulfur removal by volatiles migrating vertically to evaluate the potential of GC as a sulfur regulator. The bi-directional migration of volatiles from GC helped extend the effective distance in the horizontal direction (>15 mm), which was related to the temperature gradient. The proper temperature gradient helped the volatiles of GC spontaneously or forcedly complement the hydrogen-rich volatiles in the HOSC layer. The temperature gradient is promising to maximize the potential of GC as a sulfur regulator and break the limits on sulfur removal by GC’s volatiles.

Hydrotreating and oxidative desulfurization of heavy fuel oil into low sulfur marine fuel over dual function NiMo/γ–Al2O3 catalyst

The recent 0.5 wt% global sulfur cap on marine fuels increases the demand for low-sulfur marine fuels. Currently, marine fuels on the market contain up to 4.5 wt% of sulfur. The existing standalone desulfurization processes including hydrotreatment are not cost-effective for reducing the sulfur level of marine fuel to the mandated level. This study explored a new combination of desulfurization methods for marine fuels, first hydrotreatment under moderate process conditions, followed by oxidative desulfurization (ODS) to reduce the sulfur content to a desirable level of ≤ 0.5 wt%. The heavy fuel oil (HFO) feedstock of this study contains 3.4 wt% of S. Hydrotreating of HFO was performed in a trickle bed reactor using a commercial NiMo/γ–Al2O3 sulfide catalyst. Hydrotreating reduced the sulfur content of HFO to 1.14 wt%. It was further desulfurized by ODS using cumene hydroperoxide as an oxidant over the oxide form of NiMo/γ–Al2O3 catalyst. The FTIR analysis of the ODS product validated oxidation of sulfur compounds into sulfones and sulfoxides. The Box-Behnken design was applied to optimize ODS reaction variables such as temperature, oxidant concentration, and time. NiMo/γ–Al2O3 contains surface oxomolybdenum sites, which are expected to catalyze ODS by transferring oxygen from cumene hydroperoxide to sulfur compounds. The NiMo/γ–Al2O3 catalyst was found to be suitable for both hydrotreating and ODS. The upgraded heavy fuel oil of this two-step desulfurization process meets the IMO 2020 sulfur regulations.