A diagnostic evaluation of modeled mercury wet depositions in Europe using atmospheric speciated high-resolution observations

This study is part of the Global Mercury Observation System (GMOS), a European FP7 project dedicated to the improvement and validation of mercury models to assist in establishing a global monitoring network and to support political decisions. One key question about the global mercury cycle is the efficiency of its removal out of the atmosphere into other environmental compartments. So far, the evaluation of modeled wet deposition of mercury was difficult because of a lack of long-term measurements of oxidized and elemental mercury. The oxidized mercury species gaseous oxidized mercury (GOM) and particle-bound mercury (PBM) which are found in the atmosphere in typical concentrations of a few to a few tens pg/m³ are the relevant components for the wet deposition of mercury. In this study, the first European long-term dataset of speciated mercury taken at Waldhof/Germany was used to evaluate deposition fields modeled with the chemistry transport model (CTM) Community Multiscale Air Quality (CMAQ) and to analyze the influence of the governing parameters. The influence of the parameters precipitation and atmospheric concentration was evaluated using different input datasets for a variety of CMAQ simulations for the year 2009. It was found that on the basis of daily and weekly measurement data, the bias of modeled depositions could be explained by the bias of precipitation fields and atmospheric concentrations of GOM and PBM. A correction of the modeled wet deposition using observed daily precipitation increased the correlation, on average, from 0.17 to 0.78. An additional correction based on the daily average GOM and PBM concentration lead to a 50 % decrease of the model error for all CMAQ scenarios. Monthly deposition measurements were found to have a too low temporal resolution to adequately analyze model deficiencies in wet deposition processes due to the nonlinear nature of the scavenging process. Moreover, the general overestimation of atmospheric GOM by the CTM in combination with an underestimation of low precipitation events in the meteorological models lead to a good agreement of total annual wet deposition besides the large error in weekly deposition estimates. Moreover, it was found that the current speciation profiles for GOM emissions are the main factor for the overestimation of atmospheric GOM concentrations and might need to be revised in the future. The assumption of zero emissions of GOM lead to an improvement of the mean normalized bias for three-hourly observations of atmospheric GOM from 9.7 to 0.5, Furthermore, the diurnal correlation between model and observation increased from 0.01 to 0.64. This is a strong indicator that GOM is not directly emitted from primary sources but is mainly created by oxidation of GEM.     

Global atmospheric cycle of mercury: a model study on the impact of oxidation mechanisms

Mercury (Hg) is a global pollutant since its predominant atmospheric form, elemental Hg, reacts relatively slowly with the more abundant atmospheric oxidants. Comprehensive knowledge on the details of the atmospheric Hg cycle is still lacking, and in particular, there is some uncertainty regarding the atmospherically relevant reduction-oxidation reactions of mercury and its compounds. ECHMERIT is a global online chemical transport model, based on the ECHAM5 global circulation model, with a highly customisable chemistry mechanism designed to facilitate the investigation of both aqueous- and gas-phase atmospheric mercury chemistry. An improved version of the model which includes a new oceanic emission routine has been developed. Results of multiyear model simulations with full atmospheric chemistry have been used to examine the how changes to chemical mechanisms influence the model’s ability to reproduce measured Hg concentrations and deposition flux patterns. The results have also been compared to simple fixed-lifetime tracer simulations to constrain the possible range of atmospheric mercury redox rates. The model provides a new and unique picture of the global cycle of mercury, in that it is online and includes a full atmospheric chemistry module.     

Partition and tempospatial variation of gaseous and particulate mercury at a unique mercury-contaminated remediation site

This study investigated the seasonal variation and spatial distribution of gaseous and particulate mercury at a unique mercury-contaminated remediation site located at the near-coastal region of Tainan City, Taiwan. Gaseous elemental mercury (GEM), particulate mercury (PTM), and dustfall mercury (DFM) were measured at six nearby sites from November 2009 to September 2010. A newly issued Method for Sampling and Analyzing Mercury in Air (National Institute of Environmental Analysis [NIEA] Method A304.10C) translated from U.S. Environmental Protection Agency (EPA) Method 10-5, was applied for the measurement of atmospheric mercury in this particular study. One-year field measurements showed that the seasonal averaged concentrations of GEM and PTM were in the range of 5.56-12.60 and 0.06-0.22 ng/m3, respectively, whereas the seasonal averaged deposition fluxes of DFM were in the range of 27.0-56.8 g/km2-month. The maximum concentrations of GEM and PTM were 38.95 and 0.58 ng/m3, respectively. The atmospheric mercury apportioned as 97.42-99.87% GEM and 0.13-2.58% PTM. As a whole, the concentrations of mercury species were higher in the springtime and summertime than those in the wintertime and fall. The southern winds generally brought higher mercury concentrations, whereas the northern winds brought relatively lower mercury concentrations, to the nearby fishing villages. This study revealed that the mercury-contaminated remediation site, an abandoned chlor-alkali manufacturing plant, was the major mercury emission source that caused severe atmospheric mercury contamination over the investigation region. The hot spot of mercury emissions was allocated at the southern tip of the abandoned chlor-alkali manufacturing plant. On-site continuous monitoring of GEM at the mercury-contaminated remediation site observed that GEM concentrations during the open excavation period were 2-3 times higher than those during the nonexcavation period.     

The chemistry of atmospheric mercury: a review

The atmosphere is an important transient reservoir of mercury. In addition to its great capacity, the chemical processes transforming mercury between the elemental and divalent states strongly influence the transport characteristics and deposition rate of this toxic metal back to the ground. Modeling efforts to assess global cycling of mercury require an in-depth knowledge of atmospheric mercury chemistry. This review article provides selected physical and chemical properties of atmospheric mercury, and discusses the identified mercury transformation pathways mediated by ozone, S(IV), hydroperoxyl radical, hydroxyl radical, chlorine, nitrate radical and photolysis of Hg(II) complexes. Special attention is paid to the kinetics and mechanisms of the reactions interconverting mercury between elemental and divalent states. The significance and implications of each transformation pathway under atmospheric conditions are addressed. Future research areas that must be pursued to better understand the fate and transformation of mercury in the atmosphere are also projected.     

Seasonal variation and spatial distribution of atmospheric mercury and its gas-particulate partition in the vicinity of a semiconductor manufacturing complex

This study investigated the tempospatial variation of atmospheric mercury and its gas-particulate partition in the vicinity of a semiconductor manufacturing complex, where a plenty of flat-monitor manufacturing plants using elemental mercury as a light-initiating medium to produce backlight fluorescence tubes and may fugitively emit mercury-containing air pollutants to the atmosphere. Atmospheric mercury speciation, concentration, and the partition of total gaseous mercury (TGM) and particulate mercury (Hg_p) were measured at four sites surrounding the semiconductor manufacturing intensive district/complex. One-year field measurement showed that the seasonal averaged concentrations of TGM and Hg_p were in the range of 3.30–6.89 and 0.06–0.14 ng/m³, respectively, whereas the highest 24-h TGM and Hg_p concentrations were 10.33 and 0.26 ng/m³, respectively. Atmospheric mercury apportioned as 92.59–99.01 % TGM and 0.99–7.41 % Hg_p. As a whole, the highest and lowest concentrations of TGM were observed in the winter and summer sampling periods, respectively, whereas the concentration of Hg_p did not vary much seasonally. The highest TGM concentrations were always observed at the downwind sites, indicating that the semiconductor manufacturing complex was a hot spot of mercury emission source, which caused severe atmospheric mercury contamination over the investigation region.     

Uptake of atmospheric mercury by deionized water and aqueous solutions of inorganic salts at acidic,neutral and alkaline pH

Mercury (Hg) is well known as a toxic environmental pollutant that is among the most highly bioconcentrated trace metals in the human food chain. The atmosphere is one of the most important media for the environmental cycling of mercury, since it not only receives mercury emitted from natural sources such as volcanoes and soil and water surfaces but also from anthropogenic sources such as fossil fuel combustion, mining and metal smelting. Although atmospheric mercury exists in different physical and chemical forms, as much as 90% can occur as elemental vapour Hg0, depending on the geographic location and time of year. Atmospheric mercury can be deposited to aquatic ecosystems through both wet (rain or snow) and dry (vapour adsorption and particulate deposition) processes. The purpose of the present study was to measure, under laboratory conditions, the rate of deposition of gaseous, elemental mercury (Hg0) to deionized water and to solutions of inorganic salt species of varying ionic strengths with a pH range of 2-12. In deionized water the highest deposition rates occurred at both low (pH 2) and high (pH 12). The addition of different species of salt of various concentrations for the most part had only slight effects on the absorption and retention of atmospheric Hg0. The low pH solutions of various salt concentrations and the high pH solutions of high salt concentrations tested in this study generally showed a greater tendency to absorb and retain atmospheric Hg0 than those at a pH closer to neutral.     

Simulating Dissolved Organic Carbon Dynamics at the Swedish Integrated Monitoring Sites with the Integrated Catchments Model for Carbon,INCA-C

Surface water concentrations of dissolved organic carbon ([DOC]) are changing throughout the northern hemisphere due to changes in climate, land use and acid deposition. However, the relative importance of these drivers is unclear. Here, we use the Integrated Catchments model for Carbon (INCA-C) to simulate long-term (1996–2008) streamwater [DOC] at the four Swedish integrated monitoring (IM) sites. These are unmanaged headwater catchments with old-growth forests and no major changes in land use. Daily, seasonal and long-term variations in streamwater [DOC] driven by runoff, seasonal temperature and atmospheric sulfate (SO₄ ²⁻) deposition were observed at all sites. Using INCA-C, it was possible to reproduce observed patterns of variability in streamwater [DOC] at the four IM sites. Runoff was found to be the main short-term control on [DOC]. Seasonal patterns in [DOC] were controlled primarily by soil temperature. Measured SO₄ ²⁻ deposition explained some of the long-term [DOC] variability at all sites.     

Reconciling models and measurements to assess trends in atmospheric mercury deposition

Changes in atmospheric mercury deposition are used to evaluate the effectiveness of regulations controlling emissions. This analysis can be complicated by seemingly incongruent data from different model runs, model types, and field measurements. Here we present a case study example that describes how to identify trends in regional scale mercury deposition using best-available information from multiple data sources. To do this, we use data from three atmospheric chemistry models (CMAQ, GEOS-Chem, HYSPLIT) and multiple sediment archives (ombrotrophic bog, headwater lake, coastal salt marsh) from the Bay of Fundy region in Canada. Combined sediment and modeling data indicate that deposition attributable to US and Canadian emissions has declined in recent years, thereby increasing the relative significance of global sources. We estimate that anthropogenic emissions in the US and Canada account for 28-33% of contemporary atmospheric deposition in this region, with the rest from natural (14-32%) and global sources (41-53%).     

A screening model-based study of transport fluxes and fate of airborne mercury deposited onto catchment areas.

Dynamics of airborne mercury deposited onto catchment areas is investigated within the framework of a simulation model. Model results show that, for a particular atmospheric deposition rate, significant interannual variability in mercury transport flux in catchments is caused by climatology and corresponding differences in catchment soil loss rates; in comparison to the normal year, runoff flux increased by a factor of 2-3 for the wet year (rainfall 35% above normal) while for the dry year (rainfall 18% below normal) runoff flux decreased by factors of 5-7. The interaction of parameters describing soil type, topography and vegetation cover causes variability in both transport and emission fluxes among catchments; as soil loss rate increases by a factor of 5 due to variations in these parameters among the examined catchments, annual average transport flux increases by a factor of 3; and annual average emission flux of mercury (as Hg0) from soil to the atmosphere decreases by a factor of 2 due to the decreased levels of soil mercury associated with catchment soil loss increases. Seasonal variability of transport flux is associated with seasonal changes in precipitation and soil loss rates while seasonal changes of emission flux are primarily due to changes in soil moisture regime and temperature. Although modeled results are consistent with observational data from previous studies, they must be interpreted in a relative sense due to the screening-level character of this study.     

Mercury cycling and species mass balances in four North American lakes

A mass balance model for mercury based on the fugacity concept is applied to Lake Superior, Lake Michigan, Onondaga Lake and Little Rock Lake to evaluate model performance, analyze cycling of three mercury species groups (elemental, divalent and methyl mercury), and identify important processes that determine the source-to-concentration relationship of the three mercury species groups in these lakes. This model application to four disparate ecosystems is an extension of previous applications of fugacity-based models describing mercury cycling. The model performs satisfactorily following site-specific parameterization, and provides an estimate of minimum rates of species interconversion that compare well with literature. Volatilization and sediment burial are the main processes removing mercury from the lakes, and uncertainty analyses indicate that air-water exchange of elemental mercury and water-sediment exchange of divalent mercury attached to particles are influential in governing mercury concentrations in water. Any new model application or field campaign to quantify mercury cycling in a lake should consider these processes as important.     

Spatial and temporal variability of atmospheric mercury concentrations emitted from a coal-fired power plant in Mexico

Atmospheric mercury in the environment as a result of the consumption of fossil fuels, such as coal used in electricity generation, has gained increased attention worldwide because of its toxicity, atmospheric persistence, and bioaccumulation. Determining or predicting the concentration of this pollutant in ambient air is essential for determining sensitive areas requiring health protection. This study investigated the spatiotemporal variability of gaseous elemental mercury (GEM) concentrations and its dry deposition surrounding the Presidente Plutarco Elías Calles (CETEPEC) coal-fired power plant, located on Mexico’s Pacific coast. The CALPUFF dispersion model was applied on the basis of the daily consumption of coal during 2013 for each generating unit in the power plant and considering the local scale. The established 300-ng/m³ annual average risk factor considered by the U.S. Department of Health and Human Services (U.S. DHHS) and Integrated Risk Information System (IRIS) must not be exceeded to meet satisfactory air quality levels. An area of 65 × 60 km was evaluated, and the results show that the risk level for mercury vapor was not exceeded because the annual average concentration was 2.8 ng/m³. Although the predicted risk level was not exceeded, continuous monitoring studies of GEM and of particulates in the atmosphere, soil, and water may be necessary to identify the concentration of this pollutant, specifically that resulting from coal-fired power plants operated in environmental areas of interest in Mexico. The dry mercury deposition was low in the study area; according to the CALPUFF model, the annual average was 1.40E?2 ng/m²/sec. These results represent a starting point for Mexico’s government to implement the Minamata Convention on Mercury, which Mexico signed in 2013.

Implications: The obtained concentrations of mercury from a bigger coal-fired plant in Mexico, through the application of the CALPUFF dispersion model by the mercury emissions, are below the level recommended according to the US Department of Health and Human Services and Integrated Risk Information System. These results provide evidence of important progress in the planning and installation to the future of monitoring mercury stations in the area of interest.     

Modelling atmospheric mercury transport and deposition across Europe and the UK

There are inadequate measurements of surface ambient concentrations of mercury species and their deposition rates for the UK deposition budget to be characterized. In order to estimate the overall mercury flux budget for the UK, a simple long-term 1D Lagrangian trajectory model was constructed that treats emissions (1998), atmospheric transformation and deposition across Europe. The model was used to simulate surface concentrations of mercury and deposition across Europe at a resolution of 50 km×50 km and across the UK at 20 km×20 km. The model appeared to perform adequately when compared with the few available measurements, reproducing mean concentrations of elemental gaseous mercury at particular locations and the magnitude of regional gradients. The model showed that 68% of the UK's mercury emissions are exported and 32% deposited within the UK. Of deposition to the UK, 25% originates from the Northern Hemisphere/global background, 41% from UK sources and 33% from other European countries. The total mercury deposition to the UK is in good agreement with other modelling, 9.9 tonne yr⁻¹ cf. 9.0 tonne yr⁻¹, for 1998. However, the attribution differs greatly from the results of other coarser-scale modelling, which allocates 55% of the deposition to the UK from UK sources, 4% from other European countries and 60% from the global background atmosphere. The model was found to be sensitive to the speciation of emissions and the dry deposition velocity of elemental gaseous mercury. The uncertainties and deficiencies are discussed in terms of model parameterization and input data, and measurement data with which models can be validated. There is an urgent requirement for measurements of removal terms, concentrations, and deposition with which models can be parameterized and validated.     

Estimating atmospheric turbidity from climate data

Aerosols have several important influences on the climate system. Among the more important of these are their roles in absorbing and scattering radiation, and as condensation nuclei in cloud-forming processes. Despite their importance, knowledge of their spatial and temporal variability and, in turn, their influence on climate, is incomplete. Constraints associated with conventional approaches to measuring atmospheric turbidity – including the requirements for clear skies and costly equipment – have contributed to a paucity of turbidity data. This paper presents a methodology for estimating atmospheric turbidity from readily available surface-weather data, regardless of cloud cover. Using a high-resolution spectral radiation model, clear-sky beam irradiance is parameterized as a function of atmospheric attenuation processes, including scattering and absorption by aerosols. The model is integrated over the day to obtain an expression for estimating potential daily clear-sky beam irradiation. Turbidity can then be estimated by forcing the model with monthly averaged climate data. The methodology can be applied at any location where the requisite climate data are available and therefore holds promise for a more complete, and possibly global, climatology of aerosols.     

Modelling the dynamic air-water-sediment coupled fluxes and occurrence of polychlorinated biphenyls in a high altitude lake

The BIODEP model in terms of atmosphere-lake interactions was developed. The model was applied to an oligotrophic, dimictic high altitude lake (Lake Redo, Pyrenees) for a range of polychlorinated biphenyl (PCB) congeners. High altitude lakes, which receive their contaminant inputs uniquely from the atmosphere through long-range atmospheric transport, provide ideal controlled environments for the study of the interactions between atmospheric depositional and water column biogeochemical processes. The BIODEP model was able to predict dissolved water concentrations and PCB accumulation in the lake sediment within a factor of 2. This shows that the BIODEP model captures the essential processes driving the sink of POPs in high altitude lakes and that POP occurrence in the lake is driven by direct atmospheric inputs with limited influence from the watershed. An important seasonal variability in water column concentrations is predicted which should have important implications in sampling strategies. Furthermore, it is shown that diffusive air-water exchange dominated the PCB dynamics in the lake, especially for the less chlorinated biphenyls.     

Biogeochemistry of mercury in the Amazonian environment

In this paper, the processes that affect mercury (Hg) cycling in the Amazonian environment were reviewed, criticized and new directions of research are proposed. The discussion of the origin of the mercury contamination, whether natural or anthropogenic is marked by a lack of fundamented arguments from both sides. Undoubtedly mercury inputs from gold mining have locally increased environmental concentrations, but in the whole Amazon, these loads would be insignificant, considering the high concentrations observed by some authors in remote soils. A reasonable process that should explain these elevated concentrations in soil is that B horizons function as a mercury "sponge" that have been accumulating mercury over a geological time scale, releasing it back to cycling during erosion and forest fires. The environmental degradation of the Amazonian forest due to human activities is probably enhancing the release of that mercury to the cycle. Mercury transformations in reduced, anoxic environments--sediments and waters--are also a key problem for the understanding of the environmental methylation. The studies that have been carried out in the Amazonian environment are too restricted and results permit only circumstantial conclusions. Large efforts must be directed to monitoring programs considering time and space variability.     

The distribution of the chlorinated solvents dichloromethane,perchloroethylene, and trichloroethylene in the global atmosphere

Dichloromethane, perchloroethylene, and trichloroethylene are commercially important chlorinated solvents whose health and environmental impacts are under scrutiny in the industrial world. Their distributions in the global atmosphere have been computed based on data from the Reactive Chlorine Emissions Inventory (RCEI) project using the Global Balance Environment (GLOBE) model, a 3-D radiative-dynamical-chemical model. Their atmospheric lifetimes, scaled to an observed methyl chloroform lifetime of 4.8 years, are 158 days, 105 days, and 4.3 days, respectively. They have strong interhemispheric gradients, with maximum zonal mean surface concentrations in the winter mid-latitude northern hemisphere of approximately 40 ppt, 9 ppt, and 2.5 ppt, respectively. Their spatial distributions show significant seasonal variability, and are sensitive to vertical mixing by cumulus convection and horizontal mixing by synoptic-scale turbulence. While the model interhemispheric exchange time (1.0 years) and computed atmospheric lifetimes are very sensitive to sub-grid scale diffusion, interhemispheric gradients of the chlorinated solvents are not. The simulated results suggest a greater importance for oceanic emissions of perchloroethylene and trichloroethylene than has previously been assumed.     

Modeling of mercury emission,transport and deposition in North America

Most studies on the atmospheric behaviour of mercury in North America have excluded a detailed treatment of natural mercury emissions. The objective of this work is to report a detailed simulation of the atmospheric mercury in a domain that covers a significant part of North America and includes not only anthropogenic mercury emissions but also those from natural sources including vegetation, soil and water.The simulations were done using a natural mercury emission model coupled with the US EPA's SMOKE/CMAQ modelling system. The domain contained 132×90 grid cells at a resolution of 36 km, covering the continental United States, and major parts of Canada and Mexico. The simulation was carried out for 2002, using boundary conditions from a global mercury model. Estimated total natural mercury emission in the domain was 230 tonnes (1 tonne=1000 kg) and the ratio of natural to anthropogenic emissions varied from 0.7 in January to 3.2 in July. Average total gaseous mercury (TGM) concentration ranged between 1 and 4 ng m⁻³. Good agreement was found between the modelled results and measurements at three Ontario sites for ambient mercury concentrations, and at 72 mercury deposition network sites in the domain for wet deposition. The correlation coefficient between the simulated and the measured values of the daily average TGM at three monitoring sites varied between 0.48 and 0.64. When natural emissions were omitted, the correlation coefficients dropped to between 0.15 and 0.40. About 335 tonnes of mercury were deposited in the domain during the simulation period but overall, it acted as a net source of mercury and contributed about 21 tonnes to the global pool. The net deposition of mercury to the Great Lakes was estimated to be about 2.4 tonnes. The estimated deposition values were similar to those reported by other researchers.     

Atmospheric mercury in the Great Smoky Mountains compared to regional and global levels

Improvements in measurement technology are permitting development of a more detailed scientific understanding of the cycling of mercury in the global atmospheric environment. Critical to advancing the state of knowledge is the acquisition of accurate measurement of speciated mercury (gaseous and particulate) at ground research stations in a variety of settings located around the globe. This paper describes one such research effort conducted at TVA's Look Rock air quality monitoring site in Tennessee—a mountain top site (813 m elevation) just west of the Great Smoky Mountains National Park. The Great Smoky Mountains National Park is the largest National Park in the eastern US and it receives environmental protection under a variety of US statutes. Gaseous and particle mercury species along with some additional trace gases were measured at Look Rock during two field studies totaling 84 days in the spring and summer of 2004. Average results for the entire sampling period are: gaseous elemental mercury Hg(0): 1.65 ng m⁻³, reactive gaseous mercury RGM: 0.005 ng m⁻³, particulate mercury Hg(p): 0.007 ng m⁻³. Literature review indicates that these levels are within the range found for other rural/remote sites in North America and worldwide. Reactive and particulate mercury comprised together less than 1%, on average, of total airborne mercury at Look Rock. When compared to the global background mercury literature, the Look Rock measurements demonstrate that the atmospheric mercury levels in the vicinity of the Great Smoky Mountains National Park are clearly dominated by the global atmospheric pool, not by local or regional sources.     

Use of Stable Isotopes to Identify Sources of Mercury in Sediments: A Review and Uncertainty Analysis

Mass-dependent and mass-independent mercury isotope fractionation potentially generates unique source signatures that can be used to apportion contributions to sediment contamination. This article reviews findings from previous investigations that have used mercury isotopes to identify sources. It also discusses a mass balance mercury isotope fractionation model that simulates changes in isotopic source signatures in aquatic systems caused by natural biogeochemical cycling. According to the model, the extent of source signature alteration depends on chemical speciation, with more labile forms exhibiting greater isotopic fractionation. Apportionment is tractable when differences between δ²⁰²Hg of sources are larger than potential changes in isotopic signatures following the release of mercury into the environment.     

Time series analyses of global change data

The hypothesis that statistical analyses of historical time series data can be used to separate the influences of natural variations from anthropogenic sources on global climate change is tested. Point, regional, national, and global temperature data are analyzed. Trend analyses for the period 1901-1987 suggest mean annual temperatures increased (in degrees C per century) globally at the rate of about 0.5, in the USA at about 0.3, in the south-western USA desert region at about 1.2, and at the Walnut Gulch Experimental Watershed in south-eastern Arizona at about 0.8. However, the rates of temperature change are not constant but vary within the 87-year period. Serial correlation and spectral density analysis of the temperature time series showed weak periodicities at various frequencies. The only common periodicity among the temperature series is an apparent cycle of about 43 years. The temperature time series were correlated with the Wolf sunspot index, atmospheric CO(2) concentrations interpolated from the Siple ice core data, and atmospheric CO(2) concentration data from Mauna Loa measurements. Correlation analysis of temperature data with concurrent data on atmospheric CO(2) concentrations and the Wolf sunspot index support previously reported significant correlation over the 1901-1987 period. Correlation analysis between temperature, atmospheric CO(2) concentration, and the Wolf sunspot index for the shorter period, 1958-1987, when continuous Mauna Loa CO(2) data are available, suggest significant correlation between global warming and atmospheric CO(2) concentrations but no significant correlation between global warming and the Wolf sunspot index. This may be because the Wolf sunspot index apparently increased from 1901 until about 1960 and then decreased thereafter, while global warming apparently continued to increase through 1987. Correlation of sunspot activity with global warming may be spurious but additional analyses are required to test this hypothesis. Given the inconclusive correlation between temperature and solar activity, the significant intercorrelation between time, temperature, and atmospheric CO(2) concentrations, and the suggestion of weak periodicity in the temperature data, additional research is needed to separate the anthropogenic component from the natural variability in temperature when assessing local, regional, and global warming trends.