Risk Assessment of Mercury in Alta Floresta. Amazon Basin - Brazil

In the last 15 years gold mining activity has been the main source of the mercury (Hg) emissions into the atmosphere in the Amazon Basin. The first phase of gold production takes place in remote areas. In general the second one happens in the local urban area, where the gold is commercialized and sent to the great economic centers. In the last 3 years, this activity started to decline as a consequence of the high cost of the gold production but in the Municipality of Alta Floresta, the gold trade still plays an important role in the local economy. This paper addresses the assessment of the Hg exposure scenarios and their quantitative risk for inhalation of metallic Hg vapor and for ingestion of total Hg, using indirect exposure measurements, for different age groups of the urban area of Alta Floresta. This work took into account the field study which provided background information, such as characteristics of local and regional environment, Hg concentrations in different environmental media, and the character of the local urban population. The mean levels of Hg in the atmosphere of the urban area ranged from 210 ng/m³ to 880 ng/m³. Alta Floresta has no riverside population and there is a low fish consumption rate of 8 g/d among the general population. However, mercury levels in locally consumed carnivorous fish, ranged from 0.3 to 3.6 mg/kg, depending on the species and on the period of the year. The levels of mercury in soil surrounding the residential areas near the Hg emissions sources, ranged from 0.05 to 4.10 mg/kg. Hg in soil may represent an important source of mercury ingestion for local children up to 4 years of age. The mean Hazard Index estimated for the general adult population was 1.4. For the general population, regarding the number of persons exposed in the urban area, inhalation of metallic Hg vapor is the main route of exposure. The results for water ingestion for all groups are negligible. For families of fishermen the Hazard Index was estimated to be 9.3, with a contribution of 92% from fish ingestion.     

Mercury speciation in Lake Baikal

Research on mercury (Hg) distribution and speciation was carried out in Lake Baikal, a large, strong-oligotrophic freshwater reservoir in Siberia, Russia, during June 1992 and march 1993. In summer, total Hg in the water column ranged from 0.14 to 0.77 ng Hg/L, with the highest concentrations observed in the central basin of the lake in surface water samples. Labile inorganic Hg was found to be 7 to 20 % of the total Hg content. Highest total Hg concentrations were found in river waters: up to 2 ng Hg/L. Labile methylmercury (MeHg) concentrations ranged from 2 to 38 pg Hg/L in the water column, with the higher concentrations in the central part of the lake, and showing a slight increase in near bottom waters. Labile MeHg makes up 1 to 15 % of the total Hg content in the water column, with larger fractions in deep waters. The slight increase of the MeHg gradient with depth corresponds with the O₂ minimum region. Highest MeHg concentrations were observed in river waters (up to 145 pg Hg/L) and in some bays of the lake (up to 160 pg Hg/L). In these high temperature- and phytoplankton-rich water masses, the MeHg-fraction increased up to 35 % of total Hg. Labile MeHg concentrations in water samples taken in winter in the southern basin (under the ice cover), showed slightly higher concentrations than in summer, possibly due to an early spring bloom. In rainwater, total Hg ranged from 3 to 20 ng Hg/L and MeHg from 0.1 to 0.25 ng Hg/L. In snow, a large fraction of total Hg is bound to particulate matter; concentrations of total Hg ranged from 8 to 60 ng Hg/L and labile MeHg from 0.1 to 0.25 ng Hg/L. Atmospheric Hg was found to be 0.73 to 2.31 ng/m³ as gaseous Hg and 0.005 to 0.02 ng/m³ in its particulate form. Spatial distribution patterns of atmospheric Hg show slightly higher concentrations over the central part of the lake and the Selenga river delta. In winter, atmospheric Hg values (measured in the southern region), ranged from 1.2 to 6.1 ng/m³ as total gaseous Hg and 0.02 to 0.09 ng/m³ as total particulate Hg, and are higher than in summer, probably influenced by coal burning and traffic by the local population. MeHg contents in fish ranged from 20 ng Hg/g dry weight in small Cottocomephorus to 300 ng Hg/g dry weight in pike and trout species, which were caught in organic-rich waters.     

Ambient levels and dry deposition fluxes of mercury to Lakes Huron,Erie and St. Clair

Ambient concentrations and dry deposition fluxes of Hg in the gas and particle phase to Lakes St. Clair, Erie and Huron were estimated with a hybrid receptor-deposition model (HRD). The ambient gas and particulate phase Hg concentrations were predicted to vary by a factor of 12 to 18 during the transport of air masses traversing the lakes. The ensemble average deposition fluxes of fine particle Hg ranged from 7 pg/m²-h to 15.3 pg/m²-h over Lake St. Clair, 0.5 to 4.2 pg/m²-h over Lake Huron and 5.1 to 20.6 pg/m²-h over Lake Erie. The deposition flux of coarse particle Hg was in the range of 50 to 84 pg/m²-h over Lake St. Clair, 4.7 to 24.2 pg/m²-h over Lake Huron and 5.1 to 20.6 pg/m²-h over Lake Erie. Gaseous Hg volatilized at a rate of 0.21 to 0.52 ng/m²-h from Lake Huron and 0.13 to 0.36 from Lake Erie. Gas phase Hg was deposited at a rate of 5.9 ng/m²-h and/or volatilized at a rate of 0.5 ng/m²-h from Lake St. Clair depending upon the location of the sampling site used in the HRD model. The effect of meteorological conditions, particle size distributions and type and location of the sampling sites played an important role in the transfer of atmospheric Hg to and/or from the lakes.     

Particulate mercury in the atmosphere: Its significance,transport, transformation and sources

The importance of participate mercury (Hg(p)) in the transport, chemistry and deposition of this toxic metal has long been underestimated and largely ignored. While it was once believed to constitute a small percentage of total atmospheric mercury, Hg(p) may contribute a significant portion of the deposition of this metal to adjacent natural waters. Recent measurements of Hg(p) in several urban/industrial areas have documented that Hg can be associated with large particles (>2.5 μm) and in concentrations similar to those of the vapor phase Hg (ng/m³). As part of ongoing effort to diagnose the sources, transport and deposition of Hg to the Great Lakes and other Great Waters, the University of Michigan Air Quality Laboratory (UMAQL) has investigated the physical and chemical properties of particulate-phase Hg in both urban and rural locations. It appears that particulate Hg may be the one of the most difficult of the Hg measurements to perform, and perhaps the one of the most important for deposition and source apportionment studies. Particulate Hg concentrations measured in rural areas of the Great Lakes Region and Vermont ranged from 1 to 86 pg/m³ whereas Hg(p) levels in urban/industrialized areas were in the range 15 pg/m³ to 1.2 ng/m³.     

Occurrence and turnover of atmospheric mercury over the nordic countries

A seasonal variation of both particle and gaseous Hg concentrations in the atmosphere is present in south-western Sweden. An average gaseous Hg level of 3.7 ng m^?3 is found in winter, compared to 2.8 ng m^?3 in summer. A weak decreasing south-north gradient for gaseous Hg in air over the Nordic countries is also present, with yearly average values from 3.2 to 2.8 ng m^?3. A gradient for particulate Hg is less clear. An air parcel trajectory sector classification of gaseous Hg levels in air, and to some extent the particulate associated Hg, clearly demonstrates the increased concentrations in the southern sectors, especially in south-western Sweden where the gaseous Hg increase is about I ng m^?3. These observations are consistent with an influence from the European continent. The average concentrations of Hg in precipitation at the various stations show a pronounced decreasing south-north gradient. A major portion of the total Hg present in precipitation is associated with particles. For the southern stations, a strong correlation between Hg and sulfate, or pH, is present suggesting a connection between Hg in precipitation and anthropogenic activities.     

Denuder-based techniques for sampling,separation and analysis of gaseous and participate mercury in air

A denuder-based method for sampling and separating gaseous and participate mercury in the air is described. Two different denuder configurations developed in Vilnius, Lithuania (silver) and in Gothenburg, Sweden (gold) are compared. Data were acquired at different sampling locations around the cities of Vilnius and Gothenburg. The concentration of particulate Hg was found to be 0.04 to 0.40 ng m^?3 in the Vilnius region, and 0.11 to 0.57 ng m^?3 in the Gothenburg region. Intel-calibration results for the silver and gold denuders are presented. The results obtained by the two different denuder configurations and sampling set-ups display satisfactory agreement.     

Atmospheric Total Suspended Particulate Trace Element Identification by XRF at Ilha Grande, State of Rio De Janeiro, Brazil

Phosphorus, manganese, sulfur (S), lead, and strontium of atmospheric total suspended particulate matter, sampled during the rainy season and the dry season 2002 at the Ilha Grande Island (Rio de Janeiro State, Brazil) have been analyzed by XRF techniques. The results showed total mean concentrations of 27?±?16 ng P m^-3, 11?±?7 ng Mn m^-3, 159?±?126 ng S m^-3, 4.3?±?2.6 ng Pb m^-3, and 208?±?148 ng Sr m^-3. Generally, there is no clear influence of the two different climatic periods on the concentrations of most analyzed trace elements, with exception of sulfur the mean concentration of which, during the dry season, is about 60% higher than during the rainy season. This is probably due to biomass burning, a common practice in the Brazilian Southeast and Amazon region and/or to the presence of marine aerosols. The linear correlation coefficients strongly suggest the same source for P, Pb, and Mn. Some Pb, Mn, and P concentrations are in the range of typical values of urban areas. Potential sources of such elements are the urban and industrial emissions from the States of Rio de Janeiro and/or São Paulo.     

Mercury in forest canopy throughfall water and its relation to atmospheric deposition

A seasonal variation of both particle and gaseous Hg concentrations in the atmosphere is present in south-western Sweden. An average gaseous Hg level of 3.7 ng m⁻³ is found in winter, compared to 2.8 ng m⁻³ in summer. A weak decreasing south-north gradient for gaseous Hg in air over the Nordic countries is also present, with yearly average values from 3.2 to 2.8 ng m⁻³. A gradient for particulate Hg is less clear. An air parcel trajectory sector classification of gaseous Hg levels in air, and to some extent the particulate associated Hg, clearly demonstrates the increased concentrations in the southern sectors, especially in south-western Sweden where the gaseous Hg increase is about I ng m⁻³. These observations are consistent with an influence from the European continent. The average concentrations of Hg in precipitation at the various stations show a pronounced decreasing south-north gradient. A major portion of the total Hg present in precipitation is associated with particles. For the southern stations, a strong correlation between Hg and sulfate, or pH, is present suggesting a connection between Hg in precipitation and anthropogenic activities.     

Mercury Transport in a High-Elevation Watershed in Rocky Mountain National Park, Colorado

Mercury (Hg) was measured in stream water and precipitation in the Loch Vale watershed in Rocky Mountain National Park, Colorado, during 2001–2002 to investigate processes controlling Hg transport in high-elevation ecosystems. Total Hg concentrations in precipitation ranged from 2.6 to 36.2 ng/L and showed a strong seasonal pattern with concentrations that were 3 to 4 times higher during summer months. Annual bulk deposition of Hg was 8.3 to 12.4 μ g/m² and was similar to deposition rates in the Midwestern and Northeastern U.S. Total Hg concentrations in streams ranged from 0.8 to 13.5 ng/L and were highest in mid-May on the rising limb of the snowmelt hydrograph. Stream-water Hg was positively correlated with dissolved organic carbon suggesting organically complexed Hg was flushed into streams from near-surface soil horizons during the early stages of snowmelt. Methylmercury (MeHg) in stream water peaked at 0.048 ng/L just prior to peak snowmelt but was at or below detection (< 0.040 ng/L) for the remainder of the snowmelt season. Annual export of total Hg in Loch Vale streams ranged from 1.2 to 2.3 μ g/m², which was less than 20% of wet deposition, indicating the terrestrial environment is a net sink of atmospheric Hg. Concentrations of MeHg in stream water and corresponding watershed fluxes were low, indicating low methylation rates or high demethylation rates or both.     

Sampling and determination of gaseous and particulate mercury in the atmosphere using gold-coated denuders

Gold-coated denuders have been used to separate gas phase and particulate phase Hg in air samples. The denuders were 65 cm long with a 0.4 cm i.d. and were capable of removing >99.9% of the vapor phase elemental Hg in an air stream at flow rates of about 1 L min^?1. Data were obtained at different sampling locations around the city of Göteborg. The concentration of particulate Hg was found to be within the range of 0.11 to 0.57 ng m^?3, which corresponds to 2.8 to 16.9% of the total airborne Hg. Positive correlations between the concentration of particulate Hg and that of soot and suspended particles as well as a negative correlation between the concentration of particulate Hg and relative humidity were observed.     

Size Distribution of Trace Elements and Major Ions in the Eastern Mediterranean Atmosphere

Size distribution of trace elements is measured at the Mediterranean coast of Turkey, by analyzing hi-vol impactor samples collected between August 1993 and May 1994. Mass median diameters of marine elements are between 4.6 and 5.3 μm, and those of crustal elements are between 3.0 and 3.5 μm. Mass median diameters of crustal elements are 30% smaller in samples impacted by Saharan Dust. Pollution derived elements, As, Cd, Mo, Pb, Se, and Zn have MMD's between 1.25 and 1.01 μm. Although 70–90% of the masses of these elements were associated with particles smaller than 2.1 μm, 10–30% of their mass was associated with coarse particles. Coarse component in concentrations of Cd, Pb, Sb and particulate Hg are due to adsorption of fine anthropogenic particles on coarse crustal aerosol, whereas coarse fraction Zn, As, Se, In, Mo and Au are crustal at Al concentrations > 100 ng m^?3. Bromine, Cr, Ni, and V have bimodal distributions. The fine component, which account for approximately 30–40% of their masses are due to anthropogenic sources, whereas the coarse component, which accounts for 30–50% of their masses are due to sea salt for Br, and crustal particles for Cr, Ni, and V.     

Follow-up of mercury levels in fish,human hair and urine in the Madeira and Tapajós basins,Amazon, Brazil

Informal economy of gold mining has contaminated some important river basins in Amazon. Follow-up studies on critical compartments showed some areas with high Hg levels in fish as well as in human hair samples. Average Hg in piscivorous fish in the Madeira river itself was 846 ppb (N=284) with a maximum of 3921 ppb. Mercury in fish from non polluted areas in this basin shows high variability, even for single species. A seasonal variation in Hg content was observed, with higher values at the end of the dry season. In the upper Tapajós basin comparable values were found for fish but with a definite decreasing trend downstream. Average value for piscivorous fish in the whole Tapajós basin is 482 ppb (N=122) with a maximum value of 3770 ppb. Hair Hg was higher in fishing villages in the Tapajós (average: 17 ppm; with N=432 and maximum value of 176 ppm) than in the Madeira (average: 9 ppm; N=169; maximum 71 ppm), and data from some areas of the Tapajós suggest a decrease with time. Mercury was much higher in urine of goldshop workers in Santarém (low Tapajós) than in Alta Floresta (high Tapajbs) and show a decreasing trend in both cases, probably related to the significant decline in gold mining activities during the study period (1986–1994).     

An intensive multi-site pilot study investigating atmospheric mercury in Broward County,Florida

An intensive multi-site pilot study of atmospheric Hg was conducted in Broward County, Florida in August and September of 1993. Broward County, which contains the city of Fort Lauderdale, is located in southeastern Florida. The county borders the Florida Everglades on the west and the Atlantic Ocean on the east. A network of four sampling sites was set up for 20 days throughout Broward County to measure Hg in both the vapor phase and the particle phase as well as Hg in precipitation. The mean concentrations of total vapor phase Hg measured at two inland sites were found to be significantly higher (3.3 and 2.8 ng/m³) than that measured at a site located on the Atlantic shore (1.8 ng/m³). The mean concentrations of particle phase Hg collected at the two inland sites (51 and 49 pg/m³) were found to be 50% greater than that measured at the coastal site (34 pg/m³). In addition, event precipitation samples were collected at four sampling sites over the 20 day study period and were analyzed for both reactive and total Hg. The mean concentration of total Hg in the precipitation samples was found to be 44 ng/L, with a range of 14 to 130 ng/L. It was determined that further meteorological analysis and a more complete characterization of the aerosol and precipitation composition are needed to identify the probable source(s) contributing to the increased deposition of Hg.     

Fly ash concentrations in philadelphia aerosol determined by electron microscopy

In a study to differentiate between coal-fly ash and minerals in the atmosphere, samples were collected on Nuclepore filters in dichotomous samplers and analyzed by scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry. The samples included ambient aerosol from two sites, resuspended soil, and emissions from coal- and oil-fired power plants in the Philadelphia area. Fly ash and minerals were identified by observing high abundances of Al, Si, K, Ca, Ti, and Fe in individual particles, and their mass concentrations were estimated from measured dimensions and an assumed density. Fly ash was distinguished from minerals by morphology. Sulfate was the major component of the fine fraction (<2.5 μm aerodynamic dia.). Crustal matter concentrations in the fine fraction estimated by SEM ranged from 40 to 300 ng m^?3, and fly ash accounted for 7 to 62% of the crustal matter. In the coarse fraction (2.5 to 10 μm), minerals were the predominant component and ranged in concentration from 500 to 6000 ng m^?3. Fly ash accounted for 0 to 16% of the crustal matter; the typical amount was 6%. Other less abundant coarse particles included botanical matter and industrial source emissions. Coarse fraction crustal matter estimated from x-ray fluorescence elemental data agreed well with that based on electron microscopy.     

Mercury speciation in the Scheldt Estuary

Surface waters of the Scheldt Estuary were sampled on various occasions between 1991 and 1994. Longitudinal particulate Hg (PM) concentrations ranged from 0.4 – 1.7 μgHg/g and are essentially controlled by physical mixing of polluted fluvial particulates with relatively unpolluted marine particulates. Total dissolved mercury (TDM)concentrations ranged from 0.5 to 5.2 ng/L and are strongly influenced by removal and mobilization processes in the upper estuary, while in the lower estuary mixing processes cause a progressive decrease in TDM towards the mouth. Speciation studies showed that dissolved Hg is predominantly bound to strong complexing ligands (organic substances) in the upper estuary, but this fraction decreases with increasing salinity. In June 1993, however, the reactive mercury fraction was also high in the upper estuary. Model calculations showed that a conditional stability constant for Hg- humic acid interactions of 10¹⁹ was a good estimate for the Scheldt estuary. Dissolved methylmercury was analyzed on three occasions. Significant seasonal variations were observed with concentrations ranging from 11 to 120 pg/L in the winter and 80 to 400 pg/L in summer. Supersaturation of Hg° is observed throughout the whole estuary resulting in an estimated evasion flux of 140–1400 ng/m² day.     

Atmospheric mercury concentrations above mercury contaminated mill tailings in the Carson River Drainage Basin,NV

During processing of the historic Comstock Ore, Virginia City, NV, an estimated 5.5 × 10⁹ g of metallic mercury (Hg) were released into the Carson River Drainage Basin. The Bessels Mill site is one of at least 75 locations where Hg was used to amalgamate the gold and silver from the ore. Although the mill is no longer standing, Hg contaminated tailings attest to its past location. Mercury concentrations in samples of tailings from the Bessels Mill site are as high as 1570 μg/g. Mercury concentrations vary spatially over the site. Total Hg concentrations in air measured directly over the site are well above regional background levels (1 to 7.1 ng/m³). The highest average atmospheric Hg concentration measured at the site was 240 ng/m³ for October 1993. The estimated range of Hg flux to the atmosphere from the site was 37 to 500 ng/m² hr. Atmospheric Hg concentrations varied seasonally, diurnally and spatially. Atmospheric Hg concentrations varied as a function of Hg concentration, soil and air temperature, wind speed and surface morphology.     

Wet deposition of mercury and ambient mercury concentrations at a site in the Lake Champlain basin

The “Great Waters” program, established in the 1990 Clean Air Act Amendments, mandated that atmospheric deposition of hazardous air pollutants to Lake Champlain (including Hg) be assessed. An assessment of the magnitude and seasonal variation of atmospheric Hg deposition in the Lake Champlain basin was initiated in December 1992 with one year of event precipitation collection, as well as collection of vapor and particle phase Hg in ambient air. Samples were collected at the Vermont Monitoring Cooperative air monitoring site at the Proctor Maple Research Center in Underhill Center, VT. The average volume-weighted concentration for Hg in precipitation was 8.3 ng/L for the sampling year and the average amount of Hg deposited with each precipitation event was 0.069 μg/m². The total amount of Hg deposited through precipitation during 1993 was 9.26 μg/m²/yr. A seasonal pattern for Hg in precipitation was evident, with increased concentrations and deposition during spring and summer months. Meteorological analysis indicated the highest levels of Hg in precipitation were associated with regional transport from the south regardless of season, and with transport from the west, southwest and northwest during spring and summer months. Concentrations of ambient vapor phase Hg were typical of rural locations and consistent across seasons. Ambient particulate Hg concentrations averaged 11 pg/m³ with highest concentrations during the winter months.     

Polycyclic Aromatic Hydrocarbons and their Molecular Diagnostic Ratios in Airborne Particles (PM10) Collected in Rio de Janeiro, Brazil

Atmospheric polycyclic aromatic hydrocarbons (PAHs) were determined in particulate matter (PM10) collected in a suburban area with industrial and vehicular emissions in the Metropolitan Area of Rio de Janeiro City (Brazil). A total of 22 samples were collected between March and August 2005 by means of a high volume PM10 sampler. The particulate matter contained in the filters was extracted ultrasonically with dichloromethane. The extracts were later analyzed by gas chromatography coupled to a mass spectrometer (GC/MS). The individual concentrations of PAHs ranged between the detection limit and 0.386 ng m^?3. The PAHs concentrations observed in this study were towards the lowest end of the range of values reported for other European locations and also lower than values obtained for South America. PAHs concentrations and molecular ratios showed that light cars seem to be the main contributors to PM10 emissions, but diesel vehicles are clearly minor emission sources and industrial contributions should not be disregarded until more data are obtained.     

Particle-size distribution of PAH in the air of a remote Norway spruce forest in northern Bavaria

The aim of the present study was to elucidate thedistribution of particulate polycyclic aromatichydrocarbons (PAH) in the air of a remote Norwayspruce (Picea abies (L.) karst.) stand.The study encompassed a total of twenty differentcongeners. Particles in ambient air were alternativelycollected by two different Berner cascade impactors atthe field site in Northern Bavaria over a 14-weeksperiod from the end of April through to the end ofJuly 1994 and subsequently analyzed for their PAHcontent. The concentrations of total suspendedparticulate matter (TSP) ranged from 9–31 μg m^-3,suggesting that the field site is an area with a lowlevel of airborne particles. There was a negativerelationship of total particle concentrations with theamount of canopy precipitation due to particle washout at precipitation events. The distribution of theparticle masses on the different size fractions witha maximum in the 1-μm range is typical for remoteareas and indicates a medium-range transport. Theaerosol-bound PAH load decreased from spring sampleswith 2–4 ng m^-3 to values <1 ng m^-3 in the summersamples. Concurrently, the proportion of low molecularweight congeners in the total PAH load declined.Frequently, the highest PAH concentrations (referringto the air) were found in the 0.1–3 μm sizeseparates (accumulation mode). The results suggestthat apart from PAH input to the soil with litter, dryand wet deposition of aerosol particles is animportant pathway of PAH contamination of acid forestsoils in the Fichtelgebirge mountain range.     

Determination of atmospheric Hg by collection on iodated carbon,acid digestion and CVAFS detection

An established industrial monitoring technique has been refined to allow the accurate determination of total gaseous Hg in air at background levels (1–3 ng·m^?3). Samples are collected under vacuum through a commercially available iodide-impregnated carbon trap. For analysis, the trap is digested in a 7∶3 (v/v) mixture of HNO₃+H₂SO₄, and an aliquot of the digest analyzed by SnCl₂ reduction, dual gold amalgamation, and cold vapor atomic fluorescence spectrometric (CVAFS) detection. The traps exhibit little breakthrough (<5%) under flow rates of up to 1.0 l·min^?1 for periods up to 10 days. The mean value for the blank on the half traps was found to be 0.40±0.16 ng (n=20), resulting in a 3 α detection limit of 0.07 ng·m (1 week sample at 1.0 L·m^?3). Replicate field collections show a between-trap RSD of ± 6.4%, while field intercomparison with gold trapping resulted in 104±20% recovery in the 1–4 ng/m³ concentration range.