Seasonal dynamics of harmful algae in outer Oslofjorden monitored by microarray, qPCR, and microscopy

Monitoring of marine microalgae is important to predict and manage harmful algal blooms. Microarray Detection of Toxic ALgae (MIDTAL) is an FP7-funded EU project aiming to establish a multi-species microarray as a tool to aid monitoring agencies. We tested the suitability of different prototype versions of the MIDTAL microarray for the monthly monitoring of a sampling station in outer Oslofjorden during a 1-year period. Microarray data from two different versions of the MIDTAL chip were compared to results from cell counts (several species) and quantitative real-time PCR (qPCR; only Pseudochattonella spp.). While results from generation 2.5 microarrays exhibited a high number of false positive signals, generation 3.3 microarray data generally correlated with microscopy and qPCR data, with three important limitations: (1) Pseudo-nitzschia cells were not reliably detected, possibly because cells were not sufficiently retained during filtration or lysed during the extraction, and because of low sensitivity of the probes; (2) in the case of samples with high concentrations of non-target species, the sensitivity of the arrays was decreased; (3) one occurrence of Alexandrium pseudogonyaulax was not detected due to a 1-bp mismatch with the genus probe represented on the microarray. In spite of these shortcomings our data demonstrate the overall progress made and the potential of the MIDTAL array. The case of Pseudochattonella — where two morphologically similar species impossible to separate by light microscopy were distinguished — in particular, underlines the added value of molecular methods such as microarrays in routine phytoplankton monitoring.     

Molecular probes and microarrays for the detection of toxic algae in the genera Dinophysis and Phalacroma (Dinophyta)

Dinophysis and Phalacroma species containing diarrheic shellfish toxins and pectenotoxins occur in coastal temperate waters all year round and prevent the harvesting of mussels during several months each year in regions in Europe, Chile, Japan, and New Zealand. Toxicity varies among morphologically similar species, and a precise identification is needed for early warning systems. Molecular techniques using ribosomal DNA sequences offer a means to identify and detect precisely the potentially toxic species. We designed molecular probes targeting the 18S rDNA at the family and genus levels for Dinophysis and Phalacroma and at the species level for Dinophysis acuminata, Dinophysis acuta, and Dinophysis norvegica, the most commonly occurring, potentially toxic species of these genera in Western European waters. Dot blot hybridizations with polymerase chain reaction (PCR)-amplified rDNA from 17 microalgae were used to demonstrate probe specificity. The probes were modified along with other published fluorescence in situ hybridization and PCR probes and tested for a microarray platform within the MIDTAL project (http://www.midtal.com). The microarray was applied to field samples from Norway and Spain and compared to microscopic cell counts. These probes may be useful for early warning systems and monitoring and can also be used in population dynamic studies to distinguish species and life cycle stages, such as cysts, and their distribution in time and space.     

The study on biomass fraction estimate methodology of municipal solid waste incinerator in Korea

In Korea, the amount of greenhouse gases released due to waste materials was 14,800,000 t CO₂eq in 2012, which increased from 5,000,000 t CO₂eq in 2010. This included the amount released due to incineration, which has gradually increased since 2010. Incineration was found to be the biggest contributor to greenhouse gases, with 7,400,000 t CO₂eq released in 2012. Therefore, with regards to the trading of greenhouse gases emissions initiated in 2015 and the writing of the national inventory report, it is important to increase the reliability of the measurements related to the incineration of waste materials.

This research explored methods for estimating the biomass fraction at Korean MSW incinerator facilities and compared the biomass fractions obtained with the different biomass fraction estimation methods. The biomass fraction was estimated by the method using default values of fossil carbon fraction suggested by IPCC, the method using the solid waste composition, and the method using incinerator flue gas.

The highest biomass fractions in Korean municipal solid waste incinerator facilities were estimated by the IPCC Default method, followed by the MSW analysis method and the Flue gas analysis method. Therefore, the difference in the biomass fraction estimate was the greatest between the IPCC Default and the Flue gas analysis methods. The difference between the MSW analysis and the flue gas analysis methods was smaller than the difference with IPCC Default method. This suggested that the use of the IPCC default method cannot reflect the characteristics of Korean waste incinerator facilities and Korean MSW.

Implications: Incineration is one of most effective methods for disposal of municipal solid waste (MSW). This paper investigates the applicability of using biomass content to estimate the amount of CO₂ released, and compares the biomass contents determined by different methods in order to establish a method for estimating biomass in the MSW incinerator facilities of Korea. After analyzing the biomass contents of the collected solid waste samples and the flue gas samples, the results were compared with the Intergovernmental Panel on Climate Change (IPCC) method, and it seems that to calculate the biomass fraction it is better to use the flue gas analysis method than the IPCC method. It is valuable to design and operate a real new incineration power plant, especially for the estimation of greenhouse gas emissions.     

Fate of CL-20 in sandy soils: degradation products as potential markers of natural attenuation

Hexanitrohexaazaisowurtzitane (CL-20) is an emerging explosive that may replace the currently used explosives such as RDX and HMX, but little is known about its fate in soil. The present study was conducted to determine degradation products of CL-20 in two sandy soils under abiotic and biotic anaerobic conditions. Biotic degradation was prevalent in the slightly acidic VT soil, which contained a greater organic C content, while the slightly alkaline SAC soil favored hydrolysis. CL-20 degradation was accompanied by the formation of formate, glyoxal, nitrite, ammonium, and nitrous oxide. Biotic degradation of CL-20 occurred through the formation of its denitrohydrogenated derivative (m/z 393 Da) while hydrolysis occurred through the formation of a ring cleavage product (m/z 156 Da) that was tentatively identified as CH₂N-C(N-NO₂)-CHN-CHO or its isomer N(NO₂)CH-CHN-CO-CHNH. Due to their chemical specificity, these two intermediates may be considered as markers of in situ attenuation of CL-20 in soil.     

Public health and components of particulate matter: The changing assessment of black carbon

In 2012, the WHO classified diesel emissions as carcinogenic, and its European branch suggested creating a public health standard for airborne black carbon (BC). In 2011, EU researchers found that life expectancy could be extended four to nine times by reducing a unit of BC, vs reducing a unit of PM_2.5. Only recently could such determinations be made. Steady improvements in research methodologies now enable such judgments.

In this Critical Review, we survey epidemiological and toxicological literature regarding carbonaceous combustion emissions, as research methodologies improved over time. Initially, we focus on studies of BC, diesel, and traffic emissions in the Western countries (where daily urban BC emissions are mainly from diesels). We examine effects of other carbonaceous emissions, e.g., residential burning of biomass and coal without controls, mainly in developing countries.

Throughout the 1990s, air pollution epidemiology studies rarely included species not routinely monitored. As additional PM_2.5. chemical species, including carbonaceous species, became more widely available after 1999, they were gradually included in epidemiological studies. Pollutant species concentrations which more accurately reflected subject exposure also improved models.

Natural “interventions” - reductions in emissions concurrent with fuel changes or increased combustion efficiency; introduction of ventilation in highway tunnels; implementation of electronic toll payment systems – demonstrated health benefits of reducing specific carbon emissions. Toxicology studies provided plausible biological mechanisms by which different PM species, e.g., carbonaceous species, may cause harm, aiding interpretation of epidemiological studies.

Our review finds that BC from various sources appears to be causally involved in all-cause, lung cancer, and cardiovascular mortality, morbidity, and perhaps adverse birth and nervous system effects. We recommend that the U.S. EPA rubric for judging possible causality of PM_2.5. mass concentrations, be used to assess which PM_2.5. species are most harmful to public health.

Implications: Black carbon (BC) and correlated co-emissions appear causally related with all-cause, cardiovascular, and lung cancer mortality, and perhaps with adverse birth outcomes and central nervous system effects. Such findings are recent, since widespread monitoring for BC is also recent. Helpful epidemiological advances (using many health relevant PM_2.5 species in models; using better measurements of subject exposure) have also occurred. “Natural intervention” studies also demonstrate harm from partly combusted carbonaceous emissions. Toxicology studies consistently find biological mechanisms explaining how such emissions can cause these adverse outcomes. A consistent mechanism for judging causality for different PM_2.5 species is suggested.

A list of acronyms will be found at the end of the article.     

Formation of toxic species and precursors of PCDD/F in thermal decomposition of alpha-cypermethrin

This article examines the thermal decomposition of alpha-cypermethrin, one of the most common pyrethroid pesticides. The objective was to identify its decomposition pathways and to gain an understanding into the formation of toxic species in the environment, including those that may behave in combustion systems, especially in fires in the environment, as precursors for PCDD/F (polychlorinated dibenzo-p-dioxins and dibenzofurans). The experiments were conducted under non-oxidative conditions using a tubular reactor housed in a three-zone heating furnace and operated with a dilute stream of alpha-cypermethrin in 99.999% nitrogen. The condensable products were identified and quantitated, after being collected in a cold solvent trap and in an activated charcoal cartridge. The study revealed the formation of pollutants including precursors of toxic PCDD/F such as diphenyl ether and phenol. It was also found that the decomposition of alpha-cypermethrin involved parallel pathways of an unusual vinylcyclopropane rearrangement-cum-aromatisation reaction transforming alpha-cypermethrin and a rupture of the C(O)OC(CN) linkage. The former is similar to that occurring in the decomposition of permethrin pesticide, whereas the latter constitutes a newly discovered channel for the formation of pollutants. Density functional theory (DFT) calculations allowed us to attribute the occurrence of the second pathway to the effect of the cyanide group in significantly weakening the OC bond.     

Statistical analysis of winter ozone exceedances in the Uintah Basin,Utah, USA

Because of the confluence of several factors (persistent multiday inversions, petroleum production, and snow cover), the Uintah Basin of eastern Utah, USA, exhibits high concentrations of winter ozone. A regression analysis is presented that successfully predicts daily ozone concentration with a standard error of about 11 ppb. It also predicts with 90% accuracy whether any given day will exceed the National Ambient Air Quality Standard for ozone, 70 ppb. An analysis is introduced for calculating a “pseudo-lapse rate,” a determination of inversion intensity in the absence of sounding data. By combining the model with historical meteorological data, it is possible to make long-range predictions about ozone formation. The odds of observing no exceedance days in any given season are 38%. The odds of only three or fewer exceedance days in any given season are 46%.

Implications: This paper provides an improved understanding of the scientific underpinnings of the winter ozone phenomenon and an ability to make long-range predictions.     

Validation of a new method for measuring and continuously monitoring the efficiency of industrial flares

A new method has been developed for a direct and remote measurement of industrial flare combustion efficiency (CE). The method is based on a unique hyper-spectral or multi-spectral Infrared (IR) imager which provides a high frame rate, high spectral selectivity and high spatial resolution. The method can be deployed for short-term flare studies or for permanent installation providing real-time continuous flare CE monitoring.

In addition to the measurement of CE, the method also provides a measurement for level of smoke in the flare flame regardless of day or night. The measurements of both CE and smoke level provide the flare operator with a real-time tool to achieve “incipient smoke point” and optimize flare performance.

The feasibility of this method was first demonstrated in a bench scale test. The method was recently tested on full scale flares along with extractive sampling methods to validate the method. The full scale test included three types of flares – steam assisted, air assisted, and pressure assisted. Thirty-nine test runs were performed covering a CE range of approximately 60-100%. The results from the new method showed a strong agreement with the extractive methods (r²=0.9856 and average difference in CE measurement=0.5%).

Implications: Because industrial flares are operated in the open atmosphere, direct measurement of flare combustion efficiency (CE) has been a long-standing technological challenge. Currently flare operators do not have feedback in terms of flare CE and smoke level, and it is extremely difficult for them to optimize flare performance and reduce emissions. The new method reported in this paper could provide flare operators with real-time data for CE and smoke level so that flare operations can be optimized. In light of EPA’s focus on flare emissions and its new rules to reduce emissions from flares, this policy-relevant development in flare CE monitoring is brought to the attention of both the regulating and regulated communities.     

Future-year ozone prediction for the United States using updated models and inputs

The relationship between emission reductions and changes in ozone can be studied using photochemical grid models. These models are updated with new information as it becomes available. The primary objective of this study was to update the previous Collet et al. studies by using the most up-to-date (at the time the study was done) modeling emission tools, inventories, and meteorology available to conduct ozone source attribution and sensitivity studies. Results show future-year, 2030, design values for 8-hr ozone concentrations were lower than base-year values, 2011. The ozone source attribution results for selected cities showed that boundary conditions were the dominant contributors to ozone concentrations at the western U.S. locations, and were important for many of the eastern U.S. locations. Point sources were generally more important in the eastern United States than in the western United States. The contributions of on-road mobile emissions were less than 5 ppb at a majority of the cities selected for analysis. The higher-order decoupled direct method (HDDM) results showed that in most of the locations selected for analysis, NOx emission reductions were more effective than VOC emission reductions in reducing ozone levels. The source attribution results from this study provide useful information on the important source categories and provide some initial guidance on future emission reduction strategies.

Implications: The relationship between emission reductions and changes in ozone can be studied using photochemical grid models, which are updated with new available information. This study was to update the previous Collet et al. studies by using the most current, at the time the study was done, models and inventory to conduct ozone source attribution and sensitivity studies. The source attribution results from this study provide useful information on the important source categories and provide some initial guidance on future emission reduction strategies.     

Long-term dust aerosol production from natural sources in Iceland

Iceland is a volcanic island in the North Atlantic Ocean with maritime climate. In spite of moist climate, large areas are with limited vegetation cover where >40% of Iceland is classified with considerable to very severe erosion and 21% of Iceland is volcanic sandy deserts. Not only do natural emissions from these sources influenced by strong winds affect regional air quality in Iceland (“Reykjavik haze”), but dust particles are transported over the Atlantic ocean and Arctic Ocean >1000 km at times. The aim of this paper is to place Icelandic dust production area into international perspective, present long-term frequency of dust storm events in northeast Iceland, and estimate dust aerosol concentrations during reported dust events.

Meteorological observations with dust presence codes and related visibility were used to identify the frequency and the long-term changes in dust production in northeast Iceland. There were annually 16.4 days on average with reported dust observations on weather stations within the northeastern erosion area, indicating extreme dust plume activity and erosion within the northeastern deserts, even though the area is covered with snow during the major part of winter. During the 2000s the highest occurrence of dust events in six decades was reported. We have measured saltation and Aeolian transport during dust/volcanic ash storms in Iceland, which give some of the most intense wind erosion events ever measured.

Icelandic dust affects the ecosystems over much of Iceland and causes regional haze. It is likely to affect the ecosystems of the oceans around Iceland, and it brings dust that lowers the albedo of the Icelandic glaciers, increasing melt-off due to global warming. The study indicates that Icelandic dust may contribute to the Arctic air pollution.

Implications: Long-term records of meteorological dust observations from Northeast Iceland indicate the frequency of dust events from Icelandic deserts. The research involves a 60-year period and provides a unique perspective of the dust aerosol production from natural sources in the sub-Arctic Iceland. The amounts are staggering, and with this paper, it is clear that Icelandic dust sources need to be considered among major global dust sources. This paper presents the dust events directly affecting the air quality in the Arctic region.     

The OH-induced degradation mechanism of 4-chloro-2-methylphenoxyacetic acid (MCPA) with two forms in the water: a DFT comparison

The initial degradation mechanisms of OH and 4-chloro-2-methylphenoxyacetic acid (MCPA) including molecular form and anionic form are studied at the MPWB1K/6-311+G(3df, 2p)//MPWB1K/6-31+G(d, p) level. Possible reaction pathways of H-atom abstraction and OH addition are considered in detail. By result comparison analysis, it is found that the reaction mechanisms for OH and two forms of MCPA are different, and most reactions for anionic MCPA are easier than those for molecular MCPA. For H-atom abstraction reactions, the calculated energies show that OH abstracting H-atom from -CH₃ group of molecular MCPA is the most kinetically favorable process; the potential energy surface for anionic MCPA indicates that H-atom in -CH₂ group is slightly easier to be abstracted than that in -CH₃ group. For OH addition reactions, the addition of OH to the C1 site is the initial step for molecular MCPA and the predominant product is 4-chloro-2-methylphenol (denoted P3), while the C4 site is the most reactive site for anionic MCPA and the primary product results from the hydroxylation of the aromatic ring, which is in good agreement with the experimental observation. In additional, results from PCM calculations show that most reactions in water phase are more kinetically favorable than those in gas phase, though the mechanisms discussed above will not be changed.     

BTEX exposures in an area impacted by industrial and mobile sources: Source attribution and impact of averaging time

The impacts of emissions plumes from major industrial sources on black carbon (BC) and BTEX (benzene, toluene, ethyl benzene, xylene isomers) exposures in communities located >10 km from the industrial source areas were identified with a combination of stationary measurements, source identification using positive matrix factorization (PMF), and dispersion modeling. The industrial emissions create multihour plume events of BC and BTEX at the measurement sites. PMF source apportionment, along with wind patterns, indicates that the observed pollutant plumes are the result of transport of industrial emissions under conditions of low boundary layer height. PMF indicates that industrial emissions contribute >50% of outdoor exposures of BC and BTEX species at the receptor sites. Dispersion modeling of BTEX emissions from known industrial sources predicts numerous overnight plumes and overall qualitative agreement with PMF analysis, but predicts industrial impacts at the measurement sites a factor of 10 lower than PMF. Nonetheless, exposures associated with pollutant plumes occur mostly at night, when residents are expected to be home but are perhaps unaware of the elevated exposure. Averaging data samples over long times typical of public health interventions (e.g., weekly or biweekly passive sampling) misapportions the exposure, reducing the impact of industrial plumes at the expense of traffic emissions, because the longer samples cannot resolve subdaily plumes. Suggestions are made for ways for future distributed pollutant mapping or intervention studies to incorporate high time resolution tools to better understand the potential impacts of industrial plumes.

Implications: Emissions from industrial or other stationary sources can dominate air toxics exposures in communities both near the source and in downwind areas in the form of multihour plume events. Common measurement strategies that use highly aggregated samples, such as weekly or biweekly averages, are insensitive to such plume events and can lead to significant under apportionment of exposures from these sources.     

Evaluation of carbon emission reductions promoted by private driving restrictions based on automatic fare collection data in Beijing,China

Public transportation automatic fare collection (AFC) systems are able to continuously record large amounts of passenger travel information, providing massive, low-cost data for research on regulations pertaining to public transport. These data can be used not only to analyze characteristics of passengers’ trips but also to evaluate transport policies that promote a travel mode shift and emission reduction. In this study, models combining card, survey, and geographic information systems (GIS) data are established with a research focus on the private driving restriction policies being implemented in an ever-increasing number of cities. The study aims to evaluate the impact of these policies on the travel mode shift, as well as relevant carbon emission reductions. The private driving restriction policy implemented in Beijing is taken as an example. The impact of the restriction policy on the travel mode shift from cars to subways is analyzed through a model based on metro AFC data. The routing paths of these passengers are also analyzed based on the GIS method and on survey data, while associated carbon emission reductions are estimated. The analysis method used in this study can provide reference for the application of big data in evaluating transport policies.

Implications: Motor vehicles have become the most prevalent source of emissions and subsequently air pollution within Chinese cities. The evaluation of the effects of driving restriction policies on the travel mode shift and vehicle emissions will be useful for other cities in the future. Transport big data, playing an important support role in estimating the travel mode shift and emission reduction considered, can help related departments to estimate the effects of traffic jam alleviation and environment improvement before the implementation of these restriction policies and provide a reference for relevant decisions.     

Monitoring of carbon monoxide in residences with bulk wood pellet storage in the Northeast United States

The interest in biomass fuel is continuing to expand globally and in the northeastern United States as wood pellets are becoming a primary source of fuel for residential and small commercial systems. Wood pellets for boilers are often stored in basement storage rooms or large bag-type containers. Due to the enclosed nature of these storage areas, the atmosphere may exhibit increased levels of carbon monoxide. Serious accidents in Europe have been reported over the last decade in which high concentrations of carbon monoxide (CO) have been found in or near bulk pellet storage containers. The aim of this study was to characterize the CO concentrations in areas with indoor storage of bulk wood pellets. Data was obtained over approximately 7 months (December 2013 to June 2014) at 25 sites in New Hampshire and Massachusetts: 16 homes using wood pellet boilers with indoor pellet storage containers greater than or equal to 3 ton capacity; 4 homes with wood pellet heating systems with outdoor pellet storage; 4 homes using other heating fuels; and a university laboratory site. CO monitors were set up in homes to collect concentrations of CO in the immediate vicinity of wood pellet storage containers, and data were then compared to those of homes using fossil fuel systems. The homes monitored in this study provided a diverse set of housing stock spanning two and a half centuries of construction, with homes built from 1774 to 2013, representing a range of air exchange rates. The CO concentration data from each home was averaged hourly and then compared to a threshold of 9 ppm. While concentrations of CO were generally low for the homes studied, the need to properly design storage locations for pellets is and will remain a necessary component of wood pellet heating systems to minimize the risk of CO exposure.

Implications: This paper is an assessment of carbon monoxide (CO) exposure from bulk wood pellet storage in homes in New Hampshire and Massachusetts. Understanding the CO concentrations in homes allows for better designs for storage bins and ventilation for storage areas. Hence, uniform policies for stored wood pellets in homes, schools, and businesses can be framed to ensure occupant safety. Currently in New York State rebates for the installation of wood pellet boilers are only provided if the bulk pellet storage is outside of the home, yet states such as New Hampshire, Vermont, and Maine currently do not have these restrictions.     

Comparison of modeling with empirical calculation of diffuse and fugitive methane emissions in a Spanish landfill

One of the most significant environmental problems arising from landfills is the emission of methane into the atmosphere. In this study, methane emissions from a currently in-use Spanish landfill were modeled as well as being experimentally measured using a two-step method. The first step involved a qualitative walkover survey to detect where gases were being emitted on the surface of the landfill. The second stage comprised a quantitative analysis of these surface methane emissions at a selected number of points on the landfill surface using a specially designed flux chamber. The statistical analysis of the data obtained was based on the Sichel function and resulted in an average emission rate of 74.9 g·m^?2·day^?1, with 27.8 and 202.1 g·m^?2·day^?1 as the lower and upper limits of the 95% confidence interval, respectively. The total emission for the landfill, with an emitting surface of 335,000 m², is 9.16 × 10³ ton/yr. These values have been compared with those from three different models, with the model results being above the calculated mean emissions measured at the landfill, but below the upper confidence limit at 95%.

Implications: One of the main environmental problems arising from the presence of landfills is the emission of biogas (which mainly contains methane and carbon dioxide) into the atmosphere. Several experimental methods as well as models have been developed to quantify these emissions. In this work, the authors have compared the results obtained using experimental measurements with those provided by some local and international models using the default parameters proposed. The results obtained from the experimental method are in accordance with those provided by the models, although the models could be slightly overestimating these emissions.