Distribution and trends of mercury in aquatic and terrestrial biota of New York, USA: a synthesis of 50 years of research and monitoring.

Mercury (Hg) inputs have particularly impacted the northeastern United States due to its proximity to anthropogenic emissions sources and abundant habitats that efficiently convert inorganic Hg into methylmercury. Intensive research and monitoring efforts over the past 50 years in New York State, USA, have informed the assessment of the extent and impacts of Hg exposure on fishes and wildlife. By synthesizing Hg data statewide, this study quantified temporal trends of Hg exposure, spatiotemporal patterns of risk, the role that habitat and Hg deposition play in producing spatial patterns of Hg exposure in fish and other wildlife, and the effectiveness of current monitoring approaches in describing Hg trends. Most temporal trends were stable, but we found significant declines in Hg exposure over time in some long-sampled fish. The Adirondack Mountains and Long Island showed the greatest number of aquatic and terrestrial species with elevated Hg concentrations, reflecting an unequal distribution of exposure risk to fauna across the state. Persistent hotspots were detected for aquatic species in central New York and the Adirondack Mountains. Elevated Hg concentrations were associated with open water, forests, and rural, developed habitats for aquatic species, and open water and forested habitats for terrestrial species. Areas of consistently elevated Hg were found in areas driven by atmospheric and local Hg inputs, and habitat played a significant role in translating those inputs into biotic exposure. Continued long-term monitoring will be important in evaluating how these patterns continue to change in the face of changing land cover, climate, and Hg emissions.

Designing stimuli-responsive upconversion nanoparticles based on a mimetic immunoassay for potential accurate diabetic nephropathy diagnosis.

Diabetic nephropathy (DN) is the most common microvascular complication associated with incurable diabetes. The gold standard diagnostic method for DN is based on the detection of proteinuria but it overlooks cases of non-proteinuria (NP-DN). To address this limitation, urinary sialic acid (SA) has been confirmed as an effective biomarker for various DNs. Herein, we constructed an ultrasensitive non-proteinuria assay platform to accurately diagnose DN within 20 min. This platform utilized the ninhydrin reaction between acidic ninhydrin and urinary sialic acid (SA) as an effective biomarker for various DNs. A compound with a maximum absorption peak at 470 nm was produced in this reaction and contributed to the fluorescence decrease of the blue-emission core-shell upconverting nanoparticles through the inner filter effect (IFE). By integrating the inner filter effect (IFE) with a mimetic immunoassay, the imperceptible color was converted into highly sensitive fluorescence signals. This protocol shows a stable and high sensitivity with a detection limit of 20 nmol L-1 and provides 100% positive prediction for urine samples, demonstrating its potential for clinical diagnosis and long-term monitoring of DN.

Field Evidence for Asian Outflow and Fast Depletion of Total Gaseous Mercury in the Polluted Coastal Atmosphere.

Atmospheric mercury (Hg) cycling in polluted coastal atmosphere is complicated and not fully understood. Here, we present measurements of total gaseous mercury (TGM) monitored at a coastal mountaintop in Hong Kong downwind of mainland China. Sharp TGM peaks during cold front passages were frequently observed due to Asian pollution outflow with typical TGM/CO slopes of 6.8 ± 2.2 pg m-3 ppbv-1. Contrary to the daytime maximums of other air pollutants, TGM exhibited a distinct diurnal variation with a midday minimum. Moreover, we observed four cases of extremely fast TGM depletion after sunrise, during which TGM concentrations rapidly dipped to 0.3-0.6 ng m-3 accompanied by other pollutants on the rise. Simulated meteorological fields revealed that morning upslope flow transporting anthropogenically polluted but TGM-depleted air masses from the mixed layer caused morning TGM depletion at the mountaintop location. The TGM-depleted air masses were hypothesized to result mainly from fast photooxidation of Hg after sunrise with minor contributions from dry deposition (5.0%) and nocturnal oxidation (0.6%). A bromine-induced two-step oxidation mechanism involving abundant pollutants (NO2, O3, etc.) was estimated to play a dominant role, contributing 55%-60% of depleted TGM and requiring 0.20-0.26 pptv Br, an amount potentially available through sea salt aerosol debromination. Our findings suggest significant effects of the interaction between anthropogenic pollution and marine halogen chemistry on atmospheric Hg cycling in the coastal areas.

AIE-active Ir(III) complexes as type-I dominant photosensitizers for efficient photodynamic therapy.

The ability of a photosensitizer (PS) to generate reactive oxygen species (ROS) including type I oxygen free radicals and type II 1O2 is pivotal for photodynamic therapy. Luminescent Ir(III) complexes are effective PSs with high 1O2 generation ability owing to their high intersystem crossing ability and effective energy transfer to 3O2. However, so far, reports on type I ROS based on ˙OH generation induced by Ir(III) PS are still rare. In this work, four novel aggregation-induced emission (AIE)-active Ir(III) PSs, namely MFIriqa, MFIrqa, SFIriqa, and SFIrqa have been designed and synthesized, which show highly efficient emission in the aggregated state. Cell imaging experiment results indicate that all four Ir(III) PSs can effectively improve the signal-to-noise ratio of imaging by reducing the interference from the background due to their fascinating AIE properties. Importantly, in vitro, Ir(III) PSs MFIrqa, SFIriqa, and SFIrqa nanoparticles show obvious photodynamic activity toward cancer cells upon irradiation accompanied by type I ˙OH generation, which may be attributed to the unique excited-state characteristics of Ir(III) complexes. This work will provide guidance for the construction of a type I photosensitizer based on the AIE-active Ir(III) complex, which offers great advantages for potential clinical applications under hypoxic conditions.

Quantifying Concentrations and Emissions of Hexachlorobutadiene - A New Atmospheric Persistent Organic Pollutant in northern China.

Hexachlorobutadiene (HCBD) was listed as a new persistent organic pollutant for global regulation under Stockholm Convention in 2015, and there has been scarce information on its atmospheric concentrations, distributions, and emission sources. HCBD air samples were collected and analyzed to characterize concentrations and distributions at high elevation and urban sites as well as emission source locations in Northern China. We found ambient concentrations of HCBD in Northern China averaged at 34 ± 16 and 36 ± 28 pptv at urban sites in Jinan and Tai'an, respectively, and 31 ± 21 pptv at a high-elevation site Mount Tai. HCBD concentrations at the high elevation and urban sites were found to be affected by long-range transport under the influence of the East Asian monsoon climate. Over potential sources areas, we found concentrations of 76 ± 33 pptv in a mixed factory park, 59 ± 21 pptv in a rubber plant and 74 ± 8 pptv in a municipal solid waste (MSW) landfill area, which were all several times higher than in urban sites. The large concentration gradient across the various environments revealed strong emission sources of HCBD, especially over MSW landfill and Cl-compound production and application areas. An emission rate of 9.2 × 104 kg/yr and an oxidation rate of 32.9 kg/yr for HCBD were estimated for the mixed factory park. OH and Cl are much more active in reaction with HCBD than other oxidants in the atmosphere. Dry deposition and oxidation removed about 5.3% and 0.04%, respectively, of the emitted, suggesting that ∼95% of the emitted HCBD remaining in the atmosphere and could be transported for redistribution. Our findings revealed significant emission sources of HCBD in northern China, which was in turn affected by major sources in East-central China. The regional influence of HCBD pollution warrants serious concerns and points to the need to develop mitigation strategies.

Effects of Brownfield Remediation on Total Gaseous Mercury Concentrations in an Urban Landscape.

In order to obtain a better perspective of the impacts of brownfields on the land-atmosphere exchange of mercury in urban areas, total gaseous mercury (TGM) was measured at two heights (1.8 m and 42.7 m) prior to 2011-2012 and after 2015-2016 for the remediation of a brownfield and installation of a parking lot adjacent to the Syracuse Center of Excellence in Syracuse, NY, USA. Prior to brownfield remediation, the annual average TGM concentrations were 1.6 ± 0.6 and 1.4 ± 0.4 ng · m - 3 at the ground and upper heights, respectively. After brownfield remediation, the annual average TGM concentrations decreased by 32% and 22% at the ground and the upper height, respectively. Mercury soil flux measurements during summer after remediation showed net TGM deposition of 1.7 ng · m - 2 · day - 1 suggesting that the site transitioned from a mercury source to a net mercury sink. Measurements from the Atmospheric Mercury Network (AMNet) indicate that there was no regional decrease in TGM concentrations during the study period. This study demonstrates that evasion from mercury-contaminated soil significantly increased local TGM concentrations, which was subsequently mitigated after soil restoration. Considering the large number of brownfields, they may be an important source of mercury emissions source to local urban ecosystems and warrant future study at additional locations.

Atmospheric mercury in an eastern Chinese metropolis (Jinan).

Urban emissions are a major contributor to atmospheric Hg budgets. Continuous measurements of total gaseous mercury (TGM) and particulate-bound mercury (PHg) in PM2.5 were conducted from October 2015 to July 2016 in a metropolis, Jinan, in eastern China. Average TGM and PHg concentrations were 4.91 ± 3.66 ng m-3 and 451.9 ± 433.4 pg m-3, respectively, in the entire study period. During the winter heating period (HP), mean concentrations of TGM and PHg were 5.79 ng m-3 and 598.7 pg m-3, respectively, twice higher than those during the non-heating periods (NHPs). During the HP, TGM exhibited a distinct diurnal pattern with a peak in the morning and a minimum in the afternoon on less polluted days but a singular peak at midday on heavily polluted days. The diurnal variation of TGM during the NHPs was predominantly influenced by the variation in boundary layer height while during the HP by anthropogenic emissions. The ratio of PHg/PM2.5 in Jinan was one to two orders of magnitude larger than those elsewhere worldwide and those in soil and coal, which suggested the high enrichment of PHg in PM2.5 in Jinan. Correlation and principle component analysis results suggested that PHg and TGM had common combustion sources during the HP, whereas PHg resulted mainly from biomass burning and meteorological variations during the NHPs. High Hg concentrations in Jinan were mostly caused by emissions from coal-fired power plants, especially for those situated east of the sampling site. In addition, TGM and PHg concentrations significantly increased during haze and fog episodes, but decreased during a dust episode due possibly to strong ventilation conditions combined with partitioning of Hg between adsorption to PM2.5 and coarse dust particles.

Retraction: Sublimable cationic Ir(iii) phosphor using chlorine as a counterion for high-performance monochromatic and white OLEDs.

Retraction of 'Sublimable cationic Ir(iii) phosphor using chlorine as a counterion for high-performance monochromatic and white OLEDs' by Lei Ding et al., Chem. Commun., 2018, 54, 11761-11764.

Impacts of anthropogenic emissions and meteorology on mercury deposition over lake vs land surface in upstate New York.

Atmospheric deposition is a major input of mercury (Hg) to aquatic and terrestrial ecosystems. To evaluate Hg pollution mitigation strategies for inland lakes, the two Great Lakes (Ontario and Erie) adjacent to New York State (NYS), and rural land areas of Upstate New York, the relative contributions to atmospheric Hg deposition from anthropogenic emission reductions and meteorological variations were investigated using a regional three-dimensional chemical transport model with detailed Hg and bromine chemistry (CMAQ-newHg-Br). Our simulations suggested that NYS in-state emissions and the Northeastern US emission reductions from 2005 to 2011 did not significantly alter Hg wet and dry deposition in all study areas when averaged over time and space. However, such emission changes significantly altered intensive emission sources (>10 lb/year) with subsequent effects on deposition to nearby water bodies. For the Great Lakes, Hg dry deposition was enhanced by a factor of 2-5 in the adjacent model grids (within distances of ~12 km downwind), and the enhancements decreased to negligible values over ~50 km distances. Over land, anthropogenic emissions contributed 30% of the spatial variation in Hg dry deposition and 46% in ambient concentrations of gaseous oxidized Hg (GOM). Spatial and temporal variations in meteorology and foliar characteristics were found to affect both Hg wet and dry deposition. Convective precipitation significantly contributed to spatial and seasonal variations (~65%) in Hg wet deposition over both lake and land surfaces, whereas wind speed and surface heat flux were the main factors contributing to the spatial variation in Hg dry deposition over the lake surfaces through their impacts on dry deposition velocities of GOM and PBM. Leaf area index, which regulates deposition velocity, contributed 14% of the spatial variation in dry deposition flux over land. Variation in solar radiation, which influences photochemical formation of GOM and PBM, explained ~10% of the spatial variation over lake and land surfaces alike. Findings from our highly focused study suggested broad implications. Future climate change will likely serve to enhance Hg concentrations in biota via increases in Hg dry and wet deposition to varying degrees contingent on land surface type. Hence, liminating the health risks of Hg requires mitigation of both anthropogenic Hg emission hotspots and human-induced climate change.

Organometallic Ir(III) Phosphors Decorated by Carbazole/Diphenylphosphoryl Units for Efficient Solution-Processable OLEDs with Low Efficiency Roll-Offs.

Recently, solution-processable PhOLEDs have been attracting great interest for their low cost and high productivity relative to the vacuum-deposited devices. Similar to vacuum-deposited OLEDs, however, they usually suffer from serious efficiency roll-offs, especially in high brightness. Finding a feasible way and/or designing novel materials to increase efficiencies and reduce roll-offs simultaneously are highly desired. Herein, a new family of solution-processable cyclometalated iridium(III) phosphors with carbazole (Cz) and/or diphenylphosphoryl (Ph2PO) units functionalized main ligands has been designed. Owing to Cz and Ph2PO moieties possessing bulky steric effects, they can suppress the intermolecular strong packing and then decrease TTA effects and emission quenching. Meanwhile, the resulting OLEDs based on the designed phosphors exhibit considerable efficiencies and relatively small efficiency roll-offs. The device based on 4 containing both Cz and Ph2PO units realized a maximum current efficiency of 21.3 cd A-1, accompanied by a small roll-off. By optimization of the configuration of OLEDs, the device performance can be further enhanced, demonstrating their potential for high-performance solution-processable PhOLEDs.

PM2.5-Bound Toxic Elements in an Urban City in East China: Concentrations, Sources, and Health Risks.

Concentrations of PM2.5-bound trace elements have increased in China, with increasing anthropogenic emissions. In this study, long-term measurements of PM2.5-bound trace elements were conducted from January 2014 to January 2015 in the urban city of Jinan, east China. A positive matrix factorization model (PMF) and health risk assessment were used to evaluate the sources and health risks of these elements, respectively. Compared with most Chinese megacities, there were higher levels of arsenic, manganese, lead, chromium, and zinc in this city. Coal combustion, the smelting industry, vehicle emission, and soil dust were identified as the primary sources of all the measured elements. Heating activities during the heating period led to a factor of 1.3⁻2.8 higher concentrations for PM2.5 and all measured elements than those during the non-heating period. Cumulative non-carcinogenic and carcinogenic risks of the toxic elements exceeded the safety levels by 8⁻15 and 10⁻18 times, respectively. Arsenic was the critical element having the greatest health risk. Coal combustion caused the highest risk among the four sources. This work provides scientific data for making targeted policies to control air pollutants and protect human health.

Sublimable cationic Ir(iii) phosphor using chlorine as a counterion for high-performance monochromatic and white OLEDs.

Different from the previous design strategy, herein, a cationic Ir(iii) complex ([(ptbi)2Ir(bisq)]Cl) with a small chlorine as the counterion was synthesized, which realized the formation of a solid film via a vacuum-deposition process. The white OLED, employing it as an orange-emitting layer, achieved excellent performances with a brightness of 50 122 cd m-2, a CE of 25.5 cd A-1, an EQE of 13.1%, accompanied by a low CE efficiency roll-off of 4.7%. These are the best results among evaporated cationic Ir(iii)-based white OLEDs reported so far.

Insights on Chemistry of Mercury Species in Clouds over Northern China: Complexation and Adsorption.

Cloud effects on heterogeneous reactions of atmospheric mercury (Hg) are poorly understood due to limited knowledge of cloudwater Hg chemistry. Here we quantified Hg species in cloudwater at the summit of Mt. Tai in northern China. Total mercury (THg) and methylmercury (MeHg) in cloudwater were on average 70.5 and 0.15 ng L-1, respectively, and particulate Hg (PHg) contributed two-thirds of THg. Chemical equilibrium modeling simulations suggested that Hg complexes by dissolved organic matter (DOM) dominated dissolved Hg (DHg) speciation, which was highly pH dependent. Hg concentrations and speciation were altered by cloud processing, during which significant positive correlations of PHg and MeHg with cloud droplet number concentration ( Nd) were observed. Unlike direct contribution to PHg from cloud scavenging of aerosol particles, abiotic DHg methylation was the most likely source of MeHg. Hg adsorption coefficients Kad (5.9-362.7 L g-1) exhibited an inverse-power relationship with cloud residues content. Morphology analyses indicated that compared to mineral particles, fly ash particles could enhance Hg adsorption due to more abundant carbon binding sites on the surface. Severe particulate air pollution in northern China may bring substantial Hg into cloud droplets and impact atmospheric Hg geochemical cycling by aerosol-cloud interactions.

Distribution and sources of particulate mercury and other trace elements in PM2.5 and PM10 atop Mount Tai, China.

The concentrations of particulate mercury (PHg) and other trace elements in PM2.5 and PM10 in the atmosphere were measured at the summit of Mount Tai during the time period of 15 June - 11 August 2015. The average PHg concentrations were 83.33 ±â€¯119.1 pg/m3 for PM2.5 and 174.92 ±â€¯210.5 pg/m3 for PM10. Average concentrations for other trace elements, including Al, Ca, Fe, K, Mg, Na, Pb, As, Se, Cu, Cd, Cr, V, Mo, Co, Ag, Ba, Mn, Zn and Ni ranged from 0.06 ng/m3 (Ag) to 354.33 ng/m3 (Ca) in PM2.5 and 0.11 ng/m3 (Co) to 592.66 ng/m3 (Ca) in PM10. The average concentrations of PHg were higher than those at other domestic mountain sites and cities in other counties, lower than those at domestic city sites. Other trace elements showed concentrations lower than those at the domestic mountain sites. Due possibly to increased control of emissions and the proportion of new energy, the PHg and trace element concentrations decreased, but the PHg showed concentrations higher than those at the Mountain sites, this showed that the reasons was not only severely affected by anthropogenic emissions, but also associated with other sources. The concentration changed trend of the main trace elements indicated that PHg, trace elements and particle matters present positive correlation and fine particulate matter has a greater surface area which was conductive to adsorption of Hg and trace elements to particles. On June 19, June 27 and July 6, according to the peak of mercury and trace elements, we can predict the potential sources of these three days. The results of principal component analysis (PCA) suggested that, crustal dust, coal combustion, and vehicle emissions were the main emission sources of PHg and other trace elements in Mount Tai. The 24-h backward trajectories and potential source contribution function (PSCF) analysis revealed that air masses arriving at Mount Tai were mainly affected by Shandong province. Mount Tai was subjected to five main airflow trajectories. Clusters 1, 2, 3, and 5 represented four pathways for local and regional sources and cluster 4 originated long-distance transportation. Central Shandong was the main source regions of PHg, Pb, Se, As, Cu and Cd. Southeastern and northwestern Shandong province and northern Jiangsu province were the most polluted source regions of Mn, Zn, and Ni. The crustal elements Fe and Ca had similar distributions of potential source regions, suggested by the highest PSCF values in southeastern Shandong and northern Jiangsu.

Achieving High Performances of Nondoped OLEDs Using Carbazole and Diphenylphosphoryl-Functionalized Ir(III) Complexes as Active Components.

Nondoped electroluminescent devices offer advantages over their doped counterparts such as good reproducibility, reduced phase separation between host and guest materials, and potential of lower-cost devices. However, low luminance efficiencies and significant roll-off values are longstanding issues for nondoped devices, and a rational design strategy for the preparation of efficient phosphors is highly desired. In this work, cyclometalated Ir(III) complexes 3CzIr(mtpy), 4CzIr(mtpy), 3POIr(mtpy), and 4POIr(mtpy) bearing carbazole (Cz) or diphenylphosphoryl (Ph2PO) groups substituted at different positions of 1,2-diphenyl-H-benzimidazole (HPBI) were designed and synthesized. Owing to the steric effects induced by these groups, a significant intermolecular interaction was avoided, thereby reducing self-quenching and triplet-triplet annihilation (TTA) at high brightness. Simultaneously, attached functional moieties manipulate the charge-carrier character and enhance the EL performance of the complexes. Device N3-10, based on 3POIr(mtpy), successfully realized excellent performance and improved efficiency stability, rendering a turn-on voltage of 2.5 V, a maximum current efficiency of 29.7 cd A-1, and a maximum power efficiency of 31.1 lm W-1, which are all almost 3-fold higher than that of the control device N-10 based on parent complex. Inspiringly, all of the devices showed reduced efficiency roll-off as luminance increased. To the best of our knowledge, these are good results for green-emitting PHOLEDs using vacuum evaporation techniques, and they provide fundamental insights into the future realization of efficient phosphorescent Ir(III) complexes and corresponding nondoped devices.

Characteristics and potential sources of atmospheric particulate mercury in Jinan, China.

Measurements of atmospheric particulate mercury (PHg) were conducted at a suburban site in Jinan, China from June 2014 to December 2015. The average PHg concentration was 508.5±402.7pgm-3, and the average Hg content in PM2.5 (particles with a diameter of 2.5µm or less) was 6.60±5.82µgg-1. Both PHg and Hg content in PM2.5 aerosols were comparable to levels in some cities in China and were much higher than in cities in North America and Europe. Weak correlations were found between PHg and meteorological parameters. The correlations between PHg and other pollutants in ambient air, including SO2, CO and NOχ, together with their wind dependence were used for source analysis, which suggested coal-fired industries, cement plants and traffic emissions as potential local sources for the site. Cluster analysis of 36-h backward trajectories suggested that the regional transport from southwestern Shandong Province also contributed to PHg in Jinan.

Do we understand what the mercury speciation instruments are actually measuring? Results of RAMIX.

From August 22 to September 16, 2012, atmospheric mercury (Hg) was measured from a common manifold in the field during the Reno Atmospheric Mercury Intercomparison eXperiment. Data were collected using Tekran systems, laser induced fluorescence, and evolving new methods. The latter included the University of Washington-Detector for Oxidized Mercury, the University of Houston Mercury instrument, and a filter-based system under development by the University of Nevada-Reno. Good transmission of total Hg was found for the manifold. However, despite application of standard protocols and rigorous quality control, systematic differences in operationally defined forms of Hg were measured by the sampling systems. Concentrations of reactive Hg (RM) measured with new methods were at times 2-to-3-fold higher than that measured by Tekran system. The low RM recovery by the latter can be attributed to lack of collection as the system is currently configured. Concentrations measured by all instruments were influenced by their sampling location in-the-manifold and the instrument analytical configuration. On the basis of collective assessment of the data, we hypothesize that reactions forming RM were occurring in the manifold. Results provide a new framework for improved understanding of the atmospheric chemistry of Hg.

Air toxic emissions from snowmobiles in Yellowstone National Park.

A study on emissions associated with oversnow travel in Yellowstone National Park (YNP) was conducted for the time period of February 13-16, 2002 and February 12-16, 2003. Whole air and exhaust samples were characterized for 85 volatile organic compounds using gas chromatography. The toxics including benzene, toluene, ethylbenzene, xylenes (p-, m-, and o-xylene), and n-hexane, which are major components of two-stroke engine exhaust, show large enhancements during sampling periods resulting from increased snowmobile traffic. Evaluation of the photochemical history of air masses sampled in YNP revealed that emissions of these air toxics were (i) recent, (ii) persistent throughout the region, and (iii) consistent with the two-stroke engine exhaust sample fingerprints. The annual fluxes were estimated to be 0.35, 1.12, 0.24, 1.45, and 0.36 Gg yr(-1) for benzene, toluene, ethylbenzene, xylenes, and n-hexane, respectively, from snowmobile usage in YNP. These results are comparable to the flux estimates of 0.23, 0.77, 0.17, and 0.70 Gg yr(-1) for benzene, toluene, ethylbenzene, and xylenes, respectively, that were derived on the basis of (i) actual snowmobile counts in the Park and (ii) our ambient measurements conducted in 2003. Extrapolating these results, annual emissions from snowmobiles in the U.S. appear to be significantly higher than the values from the EPA National Emissions Inventory (1999). Snowmobile emissions represent a significant fraction ( approximately 14-21%) of air toxics with respect to EPA estimates of emissions by nonroad vehicles. Further investigation is warranted to more rigorously quantify the difference between our estimates and emission inventories.