Yanxu Zhang

Inhalation exposure to ambient polycyclic aromatic hydrocarbons and lung cancer risk of Chinese population.

An Euler atmospheric transport model (Canadian Model for Environmental Transport of Organochlorine Pesticides, CanMETOP) was applied and validated to estimate polycyclic aromatic hydrocarbon (PAH) ambient air concentrations at ground level in China based on a high-resolution emission inventory. The results were used to evaluate lung cancer risk for the Chinese population caused by inhalation exposure to PAHs. The uncertainties of the transport model, exposure, and risk analysis were assessed by using Monte Carlo simulation, taking into consideration the variation in PAH emission, aerosol and OH radical concentrations, dry deposition, respiration rate, and genetic susceptibility. The average benzo[a]pyrene equivalent concentration (B[a]Peq) was 2.43 [≈1.29–4.50 as interquartile range (IR)] ng/m3. The population-weighted B[a]Peq was 7.64 (IR, ≈4.05–14.1) ng/m3 because of the spatial overlap of the emissions and population density. It was estimated that 5.8% (IR, ≈2.0–11%) of Chinas land area, where 30% (IR, ≈17–43%) of the population lives, exceeded the national ambient B[a]Peq standard of 10 ng/m3. Taking into consideration the variation in exposure concentration, respiration rate, and susceptibility, the overall population attributable fraction (PAF) for lung cancer caused by inhalation exposure to PAHs was 1.6% (IR, ≈0.91–2.6%), corresponding to an excess annual lung cancer incidence rate of 0.65 × 10−5. Although the spatial variability was high, the lung cancer risk in eastern China was higher than in western China, and populations in major cities had a higher risk of lung cancer than rural areas. An extremely high PAF of >44% was estimated in isolated locations near small-scale coke oven operations.

Emission of Polycyclic Aromatic Hydrocarbons from Indoor Straw Burning and Emission Inventory Updating in China

The emission factors for indoor straw combustion are a major data gap for estimating the polycyclic aromatic hydrocarbon (PAH) emissions in China. The emission factors for open‐fire straw burning were borrowed from our previous study and a rough estimate was developed. As one of the most important emission sources in China, the emission factors for indoor straw combustion needed to be determined and revised accurately. In this study, a representative straw in rural China was collected and burned in similar conditions with those used by countryside families. The smoke produced was sampled and the PAH concentrations were analyzed by gas chromatography–mass selective detection (GC‐MSD), and much higher emission factors were found. Based on the newly measured emission factors, the emission amount from indoor straw combustion was updated. In addition, recently published emission factors were compiled in a comprehensive database and some new sources were included. Additionally, the emission inventory was extended to cover the period from 1950 to 2005 and upgraded to a scale resolution of one kilometer. In the updated inventory, the total quantity of 16 PAHs emitted from China was 116,000 tons in 2003, with indoor straw and firewood combustions as the most important sources. Although vehicular emission contributed a relatively small percentage of the total emission, it was still one of the major sources in the urban areas of China. The total PAH emission increased continuously for four decades, starting from 1950, but fluctuated since 1990 due to variations in coke production.

Global Biogeochemical Implications of Mercury Discharges from Rivers and Sediment Burial

Rivers are an important source of mercury (Hg) to marine ecosystems. Based on an analysis of compiled observations, we estimate global present-day Hg discharges from rivers to ocean margins are 27 ± 13 Mmol a(-1) (5500 ± 2700 Mg a(-1)), of which 28% reaches the open ocean and the rest is deposited to ocean margin sediments. Globally, the source of Hg to the open ocean from rivers amounts to 30% of atmospheric inputs. This is larger than previously estimated due to accounting for elevated concentrations in Asian rivers and variability in offshore transport across different types of estuaries. Riverine inputs of Hg to the North Atlantic have decreased several-fold since the 1970s while inputs to the North Pacific have increased. These trends have large effects on Hg concentrations at ocean margins but are too small in the open ocean to explain observed declines of seawater concentrations in the North Atlantic or increases in the North Pacific. Burial of Hg in ocean margin sediments represents a major sink in the global Hg biogeochemical cycle that has not been previously considered. We find that including this sink in a fully coupled global biogeochemical box model helps to balance the large anthropogenic release of Hg from commercial products recently added to global inventories. It also implies that legacy anthropogenic Hg can be removed from active environmental cycling on a faster time scale (centuries instead of millennia). Natural environmental Hg levels are lower than previously estimated, implying a relatively larger impact from human activity.

Seasonal variation of polycyclic aromatic hydrocarbons (PAHs) emissions in China

A regression model based on the provincial energy consumption data was developed to calculate the monthly proportions of residential energy consumption compared to the total year volume. This model was also validated by comparing with some survey and statistical data. With this model, a PAHs emission inventory with seasonal variation was developed. The seasonal variations of different sources in different regions of China and the spatial distribution of the major sources in different seasons were also achieved. The PAHs emissions were larger in the winter than in the summer, with a difference of about 1.3-folds between the months with the largest and the smallest emissions. Residential solid fuel combustion dominated the pattern of seasonal variation with the winter-time emissions as much as 1.6 times as that in the summer, while the emissions from wild fires and open fire straw burning was mainly concentrated during the spring and summer.

Observed decrease in atmospheric mercury explained by global decline in anthropogenic emissions

Significance Anthropogenic mercury poses risks to humans and ecosystems when converted to methylmercury. A longstanding conundrum has been the apparent disconnect between increasing global emissions trends and measured declines in atmospheric mercury in North America and Europe. This work shows that locally deposited mercury close to coal-fired utilities has declined more rapidly than previously anticipated because of shifts in speciation from air pollution control technology targeted at SO2 and NOx. Reduced emissions from utilities over the past two decades and the phase-out of mercury in many commercial products has led to lower global anthropogenic emissions and associated deposition to ecosystems. This implies that prior policy assessments underestimated the regional benefits of declines in mercury emissions from coal-fired utilities. Observations of elemental mercury (Hg0) at sites in North America and Europe show large decreases (∼1–2% y−1) from 1990 to present. Observations in background northern hemisphere air, including Mauna Loa Observatory (Hawaii) and CARIBIC (Civil Aircraft for the Regular Investigation of the atmosphere Based on an Instrument Container) aircraft flights, show weaker decreases (<1% y−1). These decreases are inconsistent with current global emission inventories indicating flat or increasing emissions over that period. However, the inventories have three major flaws: (i) they do not account for the decline in atmospheric release of Hg from commercial products; (ii) they are biased in their estimate of artisanal and small-scale gold mining emissions; and (iii) they do not properly account for the change in Hg0/HgII speciation of emissions from coal-fired utilities after implementation of emission controls targeted at SO2 and NOx. We construct an improved global emission inventory for the period 1990 to 2010 accounting for the above factors and find a 20% decrease in total Hg emissions and a 30% decrease in anthropogenic Hg0 emissions, with much larger decreases in North America and Europe offsetting the effect of increasing emissions in Asia. Implementation of our inventory in a global 3D atmospheric Hg simulation [GEOS-Chem (Goddard Earth Observing System-Chemistry)] coupled to land and ocean reservoirs reproduces the observed large-scale trends in atmospheric Hg0 concentrations and in HgII wet deposition. The large trends observed in North America and Europe reflect the phase-out of Hg from commercial products as well as the cobenefit from SO2 and NOx emission controls on coal-fired utilities.

Progress on Understanding Atmospheric Mercury Hampered by Uncertain Measurements

by Uncertain Measurements Daniel A. Jaffe,*,†,‡ Seth Lyman, Helen M. Amos, Mae S. Gustin, Jiaoyan Huang, Noelle E. Selin, Leonard Levin, Arnout ter Schure, Robert P. Mason, Robert Talbot, Andrew Rutter, Brandon Finley,† Lyatt Jaegle,‡ Viral Shah,‡ Crystal McClure,‡ Jesse Ambrose,† Lynne Gratz,† Steven Lindberg, Peter Weiss-Penzias, Guey-Rong Sheu, Dara Feddersen, Milena Horvat, Ashu Dastoor, Anthony J. Hynes, Huiting Mao, Jeroen E. Sonke, Franz Slemr, Jenny A. Fisher, Ralf Ebinghaus, Yanxu Zhang, and Grant Edwards⪫

Source apportionment of atmospheric mercury pollution in China using the GEOS-Chem model

China is the largest atmospheric mercury (Hg) emitter in the world. Its Hg emissions and environmental impacts need to be evaluated. In this study, Chinas Hg emission inventory is updated to 2007 and applied in the GEOS-Chem model to simulate the Hg concentrations and depositions in China. Results indicate that simulations agree well with observed background Hg concentrations. The anthropogenic sources contributed 35-50% of THg concentration and 50-70% of total deposition in polluted regions. Sensitivity analysis was performed to assess the impacts of mercury emissions from power plants, non-ferrous metal smelters and cement plants. It is found that power plants are the most important emission sources in the North China, the Yangtze River Delta (YRD) and the Pearl River Delta (PRD) while the contribution of non-ferrous metal smelters is most significant in the Southwest China. The impacts of cement plants are significant in the YRD, PRD and Central China.

Sources and pathways of polycyclic aromatic hydrocarbons transported to alert, the Canadian High Arctic.

A probabilistic function (integrated source contribution function, ISCF) based on backward air mass trajectory calculation was developed to track sources and atmospheric pathways of polycyclic aromatic hydrocarbons (PAHs) to the Canadian High Arctic station of Alert. In addition to the movement of air masses, the emission intensities at the sources and the major processes of partition, indirect photolysis, and deposition occurring on the way to the Arctic were incorporated into the ISCF. The predicted temporal trend of PAHs at Alert was validated by measured PAH concentrations throughout 2004. The PAH levels in the summer are orders of magnitude lower than those in the winter and spring when long-range atmospheric transport events occur more frequently. PAHs observed at Alert are mostly from East Asia (including Russia Far East), North Europe (including European Russia), and North America. These sources account for 25, 45, and 27% of PAHs atmospheric level at Alert, respectively. Source regions and transport pathways contributing to the PAHs contamination in the Canadian High Arctic vary seasonally. In the winter, Russia and Europe are the major sources. PAHs from these sources travel eastward and turn to the north at approximately 120 degrees E before reaching Alert, in conjunction with the well-known Arctic haze events. In the spring, PAHs from Russia and Europe first migrate to the west and then turn to the north at 60 degrees W toward Alert. The majority of PAHs in the summer are from northern Canada where they are carried to Alert via low-level transport pathways. In the fall, 70% of PAHs arriving at Alert are delivered from North American sources.

Six centuries of changing oceanic mercury

Mercury (Hg) is a global and persistent contaminant, affecting human health primarily via marine fish consumption. Large anthropogenic releases of Hg to the atmosphere by mining and coal combustion have resulted in a significant perturbation to the biogeochemical cycling of Hg. The magnitude of this perturbation and the relative roles of the ocean and land as sinks for anthropogenic Hg remain unclear. Here we use a 3-D global ocean biogeochemical model to show that surface ocean Hg concentrations have increased fourfold over the last 600 years. We find that anthropogenic Hg enters the oceans interior predominantly by absorption onto sinking organic matter particulates, which decompose and release Hg at a depth of 500–800 m, implying that the human perturbation is largest in subsurface waters of biologically productive regions. Our model simulation predicts that over the last six centuries half of emitted anthropogenic Hg has accumulated in the oceans and marine sediments.

Natural biogeochemical cycle of mercury in a global three‐dimensional ocean tracer model

We implement mercury (Hg) biogeochemistry in the offline global 3-D ocean tracer model (OFFTRAC) to investigate the natural Hg cycle, prior to any anthropogenic input. The simulation includes three Hg tracers: dissolved elemental (Hg0aq), dissolved divalent (HgIIaq), and particle-bound mercury (HgPaq). Our Hg parameterization takes into account redox chemistry in ocean waters, air-sea exchange of Hg0, scavenging of HgIIaq onto sinking particles, and resupply of HgIIaq at depth by remineralization of sinking particles. Atmospheric boundary conditions are provided by a global simulation of the natural atmospheric Hg cycle in the GEOS-Chem model. In the surface ocean, the OFFTRAC model predicts global mean concentrations of 0.16 pM for total Hg, partitioned as 80% HgIIaq, 14% Hg0aq, and 6% HgPaq. Total Hg concentrations increase to 0.38 pM in the thermocline/intermediate waters (between the mixed layer and 1000 m depth) and 0.82 pM in deep waters (below 1000 m), reflecting removal of Hg from the surface to the subsurface ocean by particle sinking followed by remineralization at depth. Our model predicts that Hg concentrations in the deep North Pacific Ocean (>2000 m) are a factor of 2–3 higher than in the deep North Atlantic Ocean. This is the result of cumulative input of Hg from particle remineralization as deep waters transit from the North Atlantic to the North Pacific on their ~2000 year journey. The model is able to reproduce the relatively uniform concentrations of total Hg observed in the old deep waters of the North Pacific Ocean (observations: 1.2 ± 0.4 pM; model: 1.1 ± 0.04 pM) and Southern Ocean (observations: 1.1 ± 0.2 pM; model: 0.8 ± 0.02 pM). However, the modeled concentrations are factors of 5–6 too low compared to observed concentrations in the surface ocean and in the young water masses of the deep North Atlantic Ocean. This large underestimate for these regions implies a factor of 5–6 anthropogenic enhancement in Hg concentrations.