Benzenepoly(carboxylic acid)s as Exclusive Intrinsic Markers to Assess Riverine Export of Dissolved Black Carbon.

Landscape fires annually generate large quantities of black carbon. The water-soluble fraction of black carbon (i.e., dissolved black carbon/DBC) is an important constituent of the dissolved organic carbon (DOC) pool, playing a crucial role in the global budget of refractory carbon and climate change. A key challenge in constraining the flux and fate of riverine DBC is to develop targeted and accurate quantification methods. Herein, we report that benzenepentacarboxylic acid (B5CA) intrinsically present in DBC can be used as an exclusive and holistic marker (representing both condensed aromatics and less-/nonaromatic fractions) for DBC quantification. B5CA was universally detected in water extractions of biochar and fire-affected soils with relatively large abundance but not produced by nonthermogenic processes. It has good mobility in the environment as it is not readily precipitated by cations or adsorbed by common geosorbents. B5CA also represents the recalcitrant components of DBC with excellent stability against photodegradation and biodegradation. Applying B5CA as the DBC marker in surface waters of the Changjiang River (i.e., the third largest river in the world), we calculate the DBC concentration in the downstream Changjiang River to be 4.8 ± 5.5% of the DOC flux. Our work provides a simple and reliable approach for the accurate quantification and source tracking of DBC in the soil and aquatic carbon pools.

Impact of the initial hydrophilic ratio on black carbon aerosols in the Arctic.

Black carbon (BC) contributes to patterns of Arctic warming, yet the initial hydrophilic ratio (IHR) of BC emitted from various sources and its impact on Arctic BC remain uncertain. With the use of a tagged tracer method of BC implemented in the global chemistry transport model GEOS-Chem, IHRs were partitioned into 7 BC combustion source categories according to the PKU-BC-v2 emission inventory. The results show that as the IHR increased, the concentration of BC decreased globally. The impact on Arctic BC was mainly reflected in the vertical profile and the burden rather than at the surface. Specifically, the greatest impact of IHR on Arctic BC appeared in summer, with the largest perturbation appearing at an altitude of approximately 600 hPa, reaching 8%. This change in BC vertical profile was mainly caused by the IHR change of wildfire combustion in Russia (44%) and Canada (51%), and the emissions from these two regions were also the two most important contributors to the BC concentration and burden in the middle and lower Arctic atmosphere in summer. In the other three seasons, anthropogenic combustion sources (oil, coal, and biomass) in East Asia, Russia, and Europe accounted for 19-40%, 14-28%, and 7-23%, respectively, of the monthly BC burden. Emissions from Russia were the most important contributor (27-43%) to the monthly BC surface concentration. Due to the large adjustment in IHR from 20% to 70%, biomass burning in Europe was shown to be the dominant contributor causing both burden (39%) and surface concentration (88%) changes in all seasons except summer.

Direct and Inverse Reduced-Form Models for Reciprocal Calculation of BC Emissions and Atmospheric Concentrations.

Atmospheric black carbon (BC) concentrations are governed by both emissions and meteorological conditions. Distinguishing these effects enables quantification of the effectiveness of emission mitigation actions by excluding meteorological effects. Here, we develop reduced-form models in both direct (RFDMs) and inverse (RFIMs) modes to estimate ambient BC concentrations. The models were developed based on outputs from multiyear simulations under three conditional scenarios with realistic or fixed emissions and meteorological conditions. We established a set of probabilistic functions (PFs) to quantify the meteorological influences. A significant two-way linear relationship between multiyear annual emissions and mean ambient BC concentrations was revealed at the grid cell scale. The correlation between them was more significant at grid cells with high emission densities. The concentrations and emissions at a given grid cell are also significantly correlated with emissions and concentrations of the surrounding areas, respectively, although to a lesser extent. These dependences are anisotropic depending on the prevailing winds and source regions. The meteorologically induced variation at the monthly scale was significantly higher than that at the annual scale. Of the major meteorological parameters, wind vectors, temperature, and relative humidity were found to most significantly affect variation in ambient BC concentrations.

Updated Global Black Carbon Emissions from 1960 to 2017: Improvements, Trends, and Drivers.

Accurate estimation of black carbon (BC) emissions is essential for assessing the health and climate impact of this pollutant. Past emission inventories were associated with high uncertainty due to data limitations, and recent information has provided a unique updating opportunity. Moreover, understanding the drivers that cause temporal emission changes is of research value. Here, we update the global BC emission estimates using new data on the activities and emission factors (EFs). The new inventory covers 73 detailed sources at 0.1° × 0.1° spatial resolution and monthly temporal resolution from 1960 to 2017. The estimated annual emissions were 32% higher than the average of several previous inventories, which was primarily due to field-measured EFs for residential stoves and differentiated EFs for motor vehicles. In addition, the updated emissions show an inverse U-shaped temporal trend, which was mainly driven by the interaction between the positive effects of population growth, per capita energy consumption, and vehicle fleet and the negative effects of residential energy switching, stove upgrading, phasing out of beehive coke ovens, and reduced EFs for vehicles and industrial processes. Urbanization caused a significant increase in urban emissions accompanied by a more significant decline in rural emissions.

Graphene oxide-induced formation of a boron-doped iron oxide shell on the surface of NZVI for enhancing nitrate removal.

The surface products have a significant influence on the reactivity of zero-valent iron-based materials. Although the enhancing effect of graphene on the reactivity of nanoscale zero-valent iron (NZVI)/graphene composites have been confirmed, the effect of graphene on the formation of surface products of NZVI is not well understood. In order to assess the effect of graphene on the structural of the outer iron oxide layers of NZVI, the NZVI was pre-oxidized by graphene oxide (ONZVI-GO). Compared with the NZVI oxidized by O2 (ONZVI-O2), ONZVI-GO was shown to be effective at NO3- removal with a high efficiency over a wide range of initial pH values. The results from characterization showed that GO could induce the formation of a tight iron oxide shell with dense spinel structures. The boron introduced during the preparation of NZVI was doped into iron oxides on the surface of ONZVI-GO. The B-O in adsorbed borate was transformed to B-B/B-Fe in the lattice structure of iron oxides, causing the formation of highly electron-deficient Lewis acid sites on the surface of ONZVI-GO, which could effectively gather NO3- and OH-, leading to the higher efficiency removal of NO3- than ONZVI-O2 over a wide range of initial pH values. This study provides new insight into the interaction between graphene and the surface species of NZVI.

Health effects of banning beehive coke ovens and implementation of the ban in China.

Environmental legislation and proper implementation are critical in environmental protection. In the past, beehive coke ovens (BCOs) were popular in China, resulting in enormous emissions of benzo[a]pyrene (BaP), a common indicator of carcinogenic polycyclic aromatic hydrocarbons. BCOs were banned by the Coal Law in 1996. Although BCO numbers have declined since the ban, they were not eliminated until 2011 due to poor implementation. Here, we present the results of a quantitative evaluation of the health effects of historical BCO operation, the health benefits of the ban, and the adverse impacts of the poor implementation of the ban. With only limited official statistics available, historical and geospatial data about BCOs were reconstructed based on satellite images. Emission inventories of BaP from BCOs were compiled and used to model atmospheric transport, nonoccupational population exposure, and induced lung cancer risk. We demonstrated that more than 20% of the BaP in ambient air was from BCOs in the peak year. The cumulative nonoccupational excess lung cancer cases associated with BaP from BCOs was 3,500 (±1,500) from 1982 to 2015. If there was no ban, the cases would be as high as 9,290 (±4,300), indicating the significant health benefits of the Coal Law. On the other hand, if the ban had been fully implemented immediately after the law was enforced in 1996, the cumulative cases would be 1,500 (±620), showing the importance of implementing the law.

Household air pollution and personal inhalation exposure to particles (TSP/PM2.5/PM1.0/PM0.25) in rural Shanxi, North China.

Personal exposure to size-segregated particles among rural residents in Shanxi, China in summer, 2011 were investigated using portable carried samplers (N = 84). Household air pollution was simultaneously studied using stationary samplers in nine homes. Information on household fuel types, cooking activity, smoking behavior, kitchen ventilation conditions etc., were also collected and discussed. The study found that even in the summer period, the daily average concentrations of PM2.5 and PM1.0 in the kitchen were as high as 376 ± 573 and 288 ± 397 µg/m3 (N = 6), that were nearly 3 times of 114 ± 81 and 97 ± 77 µg/m3 in the bedroom (N = 8), and significantly higher than those of 64 ± 28 and 47 ± 21 µg/m3 in the outdoor air (N = 6). The personal daily exposure to PM2.5 and PM1.0 were 98 ± 52 and 77 ± 47 µg/m3, respectively, that were lower than the concentrations in the kitchen but higher than the outdoor levels. The mass fractions of PM2.5 in TSP were 90%, 72%, 65% and 68% on average in the kitchen, bedroom, outdoor air and personal inhalation exposure, respectively, and moreover, a majority of particles in PM2.5 had diameters less than 1.0 µm. Calculated time-weighted average exposure based on indoor and outdoor air concentrations and time spent indoor and outdoor were positively correlated but, was ∼33% lower than the directly measured exposure. The daily exposure among those burning traditional solid fuels could be lower by ∼41% if the kitchen was equipped with an outdoor chimney, but was still 8-14% higher than those household using cleaning energies, like electricity and gas. With a ventilator in the kitchen, the exposure among the population using clean energies could be further reduced by 10-24%.

Source-oriented risk assessment of inhalation exposure to ambient polycyclic aromatic hydrocarbons and contributions of non-priority isomers in urban Nanjing, a megacity located in Yangtze River Delta, China.

Sixteen U.S. EPA priority polycyclic aromatic hydrocarbons (PAHs) and eleven non-priority isomers including some dibenzopyrenes were analyzed to evaluate health risk attributable to inhalation exposure to ambient PAHs and contributions of the non-priority PAHs in a megacity Nanjing, east China. The annual average mass concentration of the total 16 EPA priority PAHs in air was 51.1 ± 29.8 ng/m3, comprising up to 93% of the mass concentration of all 27 PAHs, however, the estimated Incremental Lifetime Cancer Risk (ILCR) due to inhalation exposure would be underestimated by 63% on average if only accounting the 16 EPA priority PAHs. The risk would be underestimated by 13% if only particulate PAHs were considered, though gaseous PAHs made up to about 70% of the total mass concentration. During the last fifteen years, ambient Benzo[a]pyrene decreased significantly in the city which was consistent with the declining trend of PAHs emissions. Source contributions to the estimated ILCR were much different from the contributions for the total mass concentration, calling for the introduce of important source-oriented risk assessments. Emissions from gasoline vehicles contributed to 12% of the total mass concentration of 27 PAHs analyzed, but regarding relative contributions to the overall health risk, gasoline vehicle emissions contributed 45% of the calculated ILCR. Dibenzopyrenes were a group of non-priority isomers largely contributing to the calculated ILCR, and vehicle emissions were probably important sources of these high molecular weight isomers. Ambient dibenzo[a,l]pyrene positively correlated with the priority PAH Benzo[g,h,i]perylene. The study indicates that inclusion of non-priority PAHs could be valuable for both PAH source apportionment and health risk assessment.

The contribution of China's emissions to global climate forcing.

Knowledge of the contribution that individual countries have made to global radiative forcing is important to the implementation of the agreement on "common but differentiated responsibilities" reached by the United Nations Framework Convention on Climate Change. Over the past three decades, China has experienced rapid economic development, accompanied by increased emission of greenhouse gases, ozone precursors and aerosols, but the magnitude of the associated radiative forcing has remained unclear. Here we use a global coupled biogeochemistry-climate model and a chemistry and transport model to quantify China's present-day contribution to global radiative forcing due to well-mixed greenhouse gases, short-lived atmospheric climate forcers and land-use-induced regional surface albedo changes. We find that China contributes 10% ± 4% of the current global radiative forcing. China's relative contribution to the positive (warming) component of global radiative forcing, mainly induced by well-mixed greenhouse gases and black carbon aerosols, is 12% ± 2%. Its relative contribution to the negative (cooling) component is 15% ± 6%, dominated by the effect of sulfate and nitrate aerosols. China's strongest contributions are 0.16 ± 0.02 watts per square metre for CO2 from fossil fuel burning, 0.13 ± 0.05 watts per square metre for CH4, -0.11 ± 0.05 watts per square metre for sulfate aerosols, and 0.09 ± 0.06 watts per square metre for black carbon aerosols. China's eventual goal of improving air quality will result in changes in radiative forcing in the coming years: a reduction of sulfur dioxide emissions would drive a faster future warming, unless offset by larger reductions of radiative forcing from well-mixed greenhouse gases and black carbon.

Global lung cancer risk from PAH exposure highly depends on emission sources and individual susceptibility.

The health impacts of polycyclic aromatic hydrocarbons (PAHs), the most concerning organic pollutants, depend not only on the locations and strengths of emission sources, but also on individual susceptibility. Moreover, trans-boundary transport makes them a global concern. In this study, a comprehensive analysis of the global health impacts of polycyclic aromatic hydrocarbons (PAHs) in ambient air is presented. Model resolution is critical in exposure modelling. Globally, incremental lifetime lung cancer risk (ILCR) induced by ambient PAH exposure is 3.1 × 10(-5). If the individual susceptibility was not taken into consideration, the overall risk would be underestimated by 55% and the proportion of highly vulnerable population would be underestimated by more than 90%. Emphasizing on individual susceptibility, our study provides an instrumental revision of current risk assessment methodology. In terms of lung cancer risk, the most important sources are combustion of biomass fuels (40%) and fossil fuels (14%) in the residential/commercial sector, coke (13%) and aluminium (12%) production, and motor vehicles (9%). PAHs can travel long distance globally especially within the Eurasian continent. Still, the risk is dominantly contributed by local.

Trend in global black carbon emissions from 1960 to 2007.

Black carbon (BC) plays an important role in both climate change and health impact. Still, BC emissions as well as the historical trends are associated with high uncertainties in existing inventories. In the present study, global BC emissions from 1960 to 2007 were estimated for 64 sources, by using recompiled fuel consumption and emission factor data sets. Annual BC emissions had increased from 5.3 (3.4-8.5 as an interquartile range) to 9.1 (5.6-14.4) teragrams during this period. Our estimations are 11-16% higher than those in previous inventories. Over the period, we found that the BC emission intensity, defined as the amount of BC emitted per unit of energy production, had decreased for all the regions, especially China and India. Improvements in combustion technology and changes in fuel composition had led to an increase in energy use efficiency, and subsequently a decline of BC emission intensities in power plants, the residential sector, and transportation. On the other hand, the BC emission intensities had increased in the industrial and agricultural sectors, mainly due to an expansion of low-efficiency industry (coke and brick production) in developing countries and to an increasing usage of diesel in agriculture in developed countries.

Exposure to ambient black carbon derived from a unique inventory and high-resolution model.

Black carbon (BC) is increasingly recognized as a significant air pollutant with harmful effects on human health, either in its own right or as a carrier of other chemicals. The adverse impact is of particular concern in those developing regions with high emissions and a growing population density. The results of recent studies indicate that BC emissions could be underestimated by a factor of 2-3 and this is particularly true for the hot-spot Asian region. Here we present a unique inventory at 10-km resolution based on a recently published global fuel consumption data product and updated emission factor measurements. The unique inventory is coupled to an Asia-nested (∼50 km) atmospheric model and used to calculate the global population exposure to BC with fully quantified uncertainty. Evaluating the modeled surface BC concentrations against observations reveals great improvement. The bias is reduced from -88% to -35% in Asia when the unique inventory and higher-resolution model replace a previous inventory combined with a coarse-resolution model. The bias can be further reduced to -12% by downscaling to 10 km using emission as a proxy. Our estimated global population-weighted BC exposure concentration constrained by observations is 2.14 µg⋅m(-3); 130% higher than that obtained using less detailed inventories and low-resolution models.

Global atmospheric emissions of polycyclic aromatic hydrocarbons from 1960 to 2008 and future predictions.

Global atmospheric emissions of 16 polycyclic aromatic hydrocarbons (PAHs) from 69 major sources were estimated for a period from 1960 to 2030. Regression models and a technology split method were used to estimate country and time specific emission factors, resulting in a new estimate of PAH emission factor variation among different countries and over time. PAH emissions in 2007 were spatially resolved to 0.1° × 0.1° grids based on a newly developed global high-resolution fuel combustion inventory (PKU-FUEL-2007). The global total annual atmospheric emission of 16 PAHs in 2007 was 504 Gg (331-818 Gg, as interquartile range), with residential/commercial biomass burning (60.5%), open-field biomass burning (agricultural waste burning, deforestation, and wildfire, 13.6%), and petroleum consumption by on-road motor vehicles (12.8%) as the major sources. South (87 Gg), East (111 Gg), and Southeast Asia (52 Gg) were the regions with the highest PAH emission densities, contributing half of the global total PAH emissions. Among the global total PAH emissions, 6.19% of the emissions were in the form of high molecular weight carcinogenic compounds and the percentage of the carcinogenic PAHs was higher in developing countries (6.22%) than in developed countries (5.73%), due to the differences in energy structures and the disparities of technology. The potential health impact of the PAH emissions was greatest in the parts of the world with high anthropogenic PAH emissions, because of the overlap of the high emissions and high population densities. Global total PAH emissions peaked at 592 Gg in 1995 and declined gradually to 499 Gg in 2008. Total PAH emissions from developed countries peaked at 122 Gg in the early 1970s and decreased to 38 Gg in 2008. Simulation of PAH emissions from 2009 to 2030 revealed that PAH emissions in developed and developing countries would decrease by 46-71% and 48-64%, respectively, based on the six IPCC SRES scenarios.

Preparation, drug release and cellular uptake of doxorubicin-loaded dextran-b-poly(ɛ-caprolactone) nanoparticles.

Amphiphilic dextran-b-poly(ɛ-caprolactone) diblock copolymers were synthesized with the purpose of preparing nanocarriers for doxorubicin (DOX), an anticancer drug. The Dex-b-PCL diblock copolymers were synthesized by end-to-end coupling of amino-terminated dextran and aldehyde-terminated poly(ɛ-caprolactone) and characterized by (1)H NMR spectra and gel permeation chromatography. The DOX-loaded Dex-b-PCL nanoparticles were prepared by a modified nanoprecipitation method and characterized by transmission electron microscopy and dynamic light scattering. In vitro release of DOX from DOX-Dex-b-PCL nanoparticles showed a sustained release manner with certain amount of burst release in the first 9h. In vitro cytotoxicity test of DOX-Dex-b-PCL nanoparticles against SH-SY5Y cells showed that DOX is still pharmacologically active after drug loading. The fluorescence imaging results showed that DOX-Dex-b-PCL nanoparticles could be easily uptaken by SH-SY5Y cells. These results indicate that DOX-Dex-b-PCL nanoparticles may be a promising nanocarrier for DOX.

Black carbon emissions in China from 1949 to 2050.

Black carbon (BC) emissions from China are of global concern. A new BC emission inventory (PKU-BC(China)) has been developed with the following improvements: (1) The emission factor database was updated; (2) a 0.1° × 0.1° gridded map was produced for 2007 based on county-level proxies; (3) time trends were derived for 1949-2007 and predicted for 2008-2050; and (4) the uncertainties associated with the inventory were quantified. It was estimated that 1957 Gg of BC were emitted in China in 2007, which is greater than previously reported. Residential coal combustion was the largest source, followed by residential biofuel burning, coke production, diesel vehicles, and brick kilns. By using a county-level disaggregation method, spatial bias in province-level disaggregation, mainly due to uneven per capita emissions within provinces, was reduced by 42.5%. Emissions increased steadily since 1949 until leveling off in the mid-1990s, due to a series of technological advances and to socioeconomic progress. BC emissions in China in 2050 are predicted to be 920-2183 Gg/yr under various scenarios; and the industrial and transportation sectors stand to benefit the most from technological improvements.

Occurrence and exposure to polycyclic aromatic hydrocarbons and their derivatives in a rural Chinese home through biomass fuelled cooking.

The concentration and composition of PAHs emitted from biomass cooking fuel were characterized in a rural non-smoking household in northern China. Twenty-two parent PAHs (pPAHs), 12 nitro-PAHs (nPAHs), and 4 oxy-PAHs (oPAHs) were measured in the kitchen, bedroom, and outdoors during both summer and winter. The most severe contamination occurred in the kitchen in the winter, where the daily mean concentrations of pPAHs, nPAHs, and oPAHs were 7500 ± 4100, 38 ± 29, and 8400 ± 9200 ng/m(3), respectively. Our results suggest that the nPAHs were largely from secondary formation in ambient air while oPAHs were either from primary emission of biomass burning or secondary formation from pPAHs in the kitchen. The daily mean benzo(a)pyrene equivalent exposure concentration was as high as 200 ± 160 ng/m(3) in the winter for the housewife who did the cooking compared to 59 ± 37 ng/m(3) for the control group that did not cook.

Organochlorine pesticides contaminated surface soil as reemission source in the Haihe Plain, China.

A large amount of organochlorine pesticides (OCPs) including hexachlorocyclohexane isomers (alpha-HCH, beta-HCH, gamma-HCH, and 6-HCH,sigmaHCH asthe total) and dichlorodiphenyltrichloroethane and metabolites (p,p'-DDT, p,p'-DDE, and p,p'-DDD, sigmaDDT as the total) have been applied over the Haihe Plain (an area of 300 000 km2) in Northern China. Even though the agricultural application of these OCPs was terminated more than a decade ago, their residues remain in the environment and continue to represent significant public health concern. In this study, more than 300 surface soil samples were collected from the Haihe Plain for measurement of these OCPs. The measured sigmaHCH and sigmaDDT residues were 3.9 +/- 26 and 64 +/- 260 ng/g as arithmetic means and standard deviations with median values of 0.38 and 6.5 ng/g, respectively. Although the levels were approximately 1 order of magnitude lower than those recorded in 1980s, it was estimated that there were 430 +/- 110 tons of sigmaHCH and 6100 +/- 760 tons of sigmaDDT in the surface soil of the area, respectively. The soils with high levels of OCP residuals were mostly distributed on the fringes of major cities, due to intensive farming and discharge from pesticide producers in the cities. The residuals of sigmaHCHs and sigmaDDTs were significantly correlated to soil organic matter content. Both alpha-HCH/beta-HCH and p,p'-DDT/p,p'-DDE ratios were log-normally distributed and negatively correlated to log(sigmaHCH) and log(sigmaDDT), respectively. Thus these ratios and correlations preclude certainty in distinguishing fresh application from historical usage. According to the total residuals and the distributions of alpha-HCH/beta-HCH and p,p'-DDT/p,p'-DDE ratios, it appears that significant recent input of either the OCPs is very unlikely. The calculated fugacities in soil and air provided quantitative evidence indicating a net and seasonally varied transport of sigmaHCH (0.31 ton/year) and sigmaDDT (1.9 ton/year) from soil to atmosphere in the study area. Such a surface-to-air transport suggested that after the ban, the surface soil had gradually converted from a major sink to an important emission source of OCPs and the reemission will continue for many years to come.