Ultraviolet absorbance as a proxy for total dissolved mercury in streams

Stream water samples were collected over a range of hydrologic and seasonal conditions at three forested watersheds in the northeastern USA. Samples were analyzed for dissolved total mercury (THg_d), DOC concentration and DOC composition, and UV₂₅₄ absorbance across the three sites over different seasons and flow conditions. Pooling data from all sites, we found a strong positive correlation of THg_d to DOC (r² = 0.87), but progressively stronger correlations of THg_d with the hydrophobic acid fraction (HPOA) of DOC (r² = 0.91) and with UV₂₅₄ absorbance (r² = 0.92). The strength of the UV₂₅₄ absorbance-THg_d relationship suggests that optical properties associated with dissolved organic matter may be excellent proxies for THg_d concentration in these streams. Ease of sample collection and analysis, the potential application of in-situ optical sensors, and the possibility for intensive monitoring over the hydrograph make this an effective, inexpensive approach to estimate THg_d flux in drainage waters.     

Effects of sediment composition on inorganic mercury partitioning, speciation and bioavailability in oxic surficial sediments

Artificially prepared sediments were used to assess the effects of sediment composition on inorganic Hg partitioning, speciation and bioavailability. Organic coating in sediment greatly increased the Hg partitioning and the amount of bioavailable Hg bound with the clay and the Fe and Mn oxides, but had little effect on that bound with the quartz and calcium carbonate as a result of weaker binding of humic acids and fulvic acids. The clay content increased the concentration of Hg in the sediments but inhibited the gut juice extraction due to the strong binding of Hg-organic matter (OM) complexes. Most Hg in the sediments was complexed by OM (mainly distributed in the organo-complexed phase and the strongly complexed phase), and the Hg-OM complexes (especially Hg in the strongly complexed phase) in sediments contributed much to gut juice extraction. Redistribution of Hg-OM complexes between sediments and gut juices may occur during gut juice extraction and modify Hg bioavailability and speciation in sediments.     

Differential partitioning and speciation of Hg in wet FGD facilities of two Spanish PCC power plants

This paper evaluates the speciation and partitioning of mercury in two Spanish pulverised coal combustion power plants (PP1 and PP2), equipped with wet limestone-based flue gas desulphurisation facilities (FGD) operating with forced oxidation and re-circulation of FGD water streams. These plants are fed with coal (PP1) and coal/pet-coke blends (PP2) with different mercury contents. The behaviour, partitioning and speciation of Hg were found to be similar during the combustion processes but different in the FGD systems of the two power plants. A high proportion (86-88%) of Hg escaped the electrostatic precipitator in gaseous form, Hg²⁺ being the predominant mercury species (68-86%) to enter the FGD. At this point, a relatively high total Hg retention (72% and 65%) was achieved in the PP1 and PP2 (2007) FGD facilities respectively. However, during the second sampling campaign for PP2 (2008), the mercury removal achieved by the FGD was much lower (26%). Lab-scale tests point to liquid/gas ratio as the main parameter affecting oxidised mercury capture in the scrubber. The partitioning of the gaseous mercury reaching the FGD system in the wastes and by-products differed. In the low mercury input power plant (PP1) most of the mercury (67%) was associated with the FGD gypsum. Moreover in PP2 a significant proportion of the gaseous mercury reaching the FGD system remained in the aqueous phase (45%) in the 2007 sampling campaign while most of it escaped in 2008 (74%). This may be attributed to the scrubber operating conditions and the different composition and chemistry of the scrubber solution probably due to the use of an additive.     

Speciation of methylmercury in rice grown from a mercury mining area

Monomethylmercury (CH₃Hg⁺ and its complexes; MeHg hereafter) is a known developmental neurotoxin. Recent studies have shown that rice (Oryza sativa L.) grain grown from mercury (Hg) mining areas may contain elevated MeHg concentrations, raising concerns over the health of local residents who consume rice on a daily basis. An analytical method employing high performance liquid chromatography (HPLC) - inductively coupled plasma mass spectrometry (ICP-MS) following enzymatic hydrolysis was developed to analyze the speciation of MeHg in uncooked and cooked white rice grain grown from the vicinity of a Hg mine in China. The results revealed that the MeHg in the uncooked rice is present almost exclusively as CH₃Hg-l-cysteinate (CH₃HgCys), a complex that is thought to be responsible for the transfer of MeHg across the blood-brain and placental barriers. Although cooking does not change the total Hg or total MeHg concentration in rice, no CH₃HgCys is measurable after cooking, suggesting that most, if not all, of the CH₃HgCys is converted to other forms of MeHg, the identity and toxicity of which remain elusive.     

Toxic substances in rivers and streams

Many of the toxic substances entering freshwaters today are those which were present several decades ago, but others have become significant recently. The effects of toxicants in flowing waters are modified by unidirectional transport and dispersion which afford the potential for a degree of 'self-purification'. The chemical quality of the receiving water also affects toxicity. Biological factors also contribute to the ultimate effect of pollutants. The potential for accumulation of toxic substances within tissues increases the significance of certain pollutants which may be present in water even though ambient concentrations are very low. The biota of flowing waters may be restored, following catastrophic entry of pollutants, by drift from unaffected regions upstream. The range of potential toxic substances is very extensive and includes inorganic poisons, organic poisons, heavy metals, pesticides and PCBs. Metals, pesticides and PCBs have the greatest potential for bioaccumulation. Few generalisations can be made regarding the effects of toxic substances on the biota. Each species tends to respond to different toxicants in different ways and even at different stages in its life-history. Toxicity tests conducted under controlled laboratory conditions sometimes produce conflicting results: it is not then to be unexpected that field observations should sometimes vary widely. Determinations of toxicity in laboratory tests must be applied with caution to field conditions and it is not wise to extrapolate findings to other species or environments.     

Solving mercury (Hg) speciation in soil samples by synchrotron X-ray microspectroscopic techniques

Direct mercury (Hg) speciation was assessed for soil samples with a Hg concentration ranging from 7 up to 240 mg kg⁻¹. Hg chemical forms were identified and quantified by sequential extractions and bulk- and micro-analytical techniques exploiting synchrotron generated X-rays. In particular, microspectroscopic techniques such as μ-XRF, μ-XRD and μ-XANES were necessary to solve bulk Hg speciation, in both soil fractions <2 mm and <2 μm. The main Hg-species found in the soil samples were metacinnabar (β-HgS), cinnabar (α-HgS), corderoite (Hg₃S₂Cl₂), and an amorphous phase containing Hg bound to chlorine and sulfur. The amount of metacinnabar and amorphous phases increased in the fraction <2 μm. No interaction among Hg-species and soil components was observed. All the observed Hg-species originated from the slow weathering of an inert Hg-containing waste material (K106, U.S. EPA) dumped in the area several years ago, which is changing into a relatively more dangerous source of pollution.     

Levels and speciation of arsenic in the atmosphere in Beijing, China

Arsenic levels and speciation in the total suspended particles (TSPs) were quantitatively determined by high performance liquid chromatography on-line coupled with hydride generation atomic fluorescence spectrometry in Beijing, China from February 2009 to March 2011. The high TSP levels fluctuated between 0.07 and 0.79 mg m⁻³, with a mean level of 0.32 ± 0.17 mg m⁻³. The total arsenic concentrations ranged from 0.03 to 0.31 μg m⁻³ (mean: 0.13 ± 0.06 μg m⁻³) in Beijing‘s air. The concentrations of As(III) and As(V) ranged from 0.73 to 20 ng m⁻³ (mean: 4.7 ± 3.6 ng m⁻³) and from 14 to 2.5 × 10² ng m⁻³ (mean: 67 ± 35 ng m⁻³), respectively. As levels and speciation demonstrated relative higher levels in spring and autumn and lower values in summer and winter. As(V) accounted for 81-99% of the extractable species in the TSP samples which showed that As(V) was the major fraction of the extractable As. Organoarsenic species, monomethylarsonate (MMA) and dimethylarsinate (DMA) were not found in all samples. Higher values of enrichment factors demonstrated that arsenic in TSP mainly come from anthropogenic sources. High As and its species levels in air and respiratory exposure (0.30-0.84 μg d⁻¹) attributed to higher excess cancer risk ((4.2 ± 2.0) × 10⁻⁴) for people in Beijing.     

Determinants of exposure to mercury in hair from inhabitants of the largest mercury mine in the world

Mercury exposure of the local population was assessed in two areas of the Almadén mercury mining district, Spain, which has been the world’s largest producer of this element. Two groups, who are exposed to different sources of mercury, from a point source in Almadén and a diffuse source hundreds of kilometres away in the same region, were studied. Total mercury (THg) in human hair ranged from 0.20 to 9.35 mg kg⁻¹ and the mean value was 2.64 mg kg⁻¹. About 87% of subjects had THg levels in excess of the EPA reference dose (RfD = 1.0 mg kg⁻¹), while a high percentage (68%) of them live in Almadén. There was a clear increase in hair Hg with reported fish consumption and the highest mean hair mercury level was 4 times the RfD in a group who had reported the highest consumption of fish. For the whole group, there was a significant effect of age, gender and fish consumption in relation to Hg concentration in the hair. Nevertheless, when both groups were tested separately by means of a multivariate regression model, there was significant exposure in those living near the mine area. Several factors such as age, gender and fish consumption remained statistically significant and were associated with THg. The main conclusion is that people living close to the hot spot are more impacted by mercury than people living further away. The intake of Hg through consumption of fish is an important parameter for Hg exposure; however, in the case of people living close to the hot spot, their levels are related to the highly Hg-impacted living environment.     

Isolating the impact of sediment toxicity in urban streams

Several factors can contribute to the ecological degradation of stream catchments following urbanization, but it is often difficult to separate their relative importance. We isolated the impact of polluted sediment on the condition of an urban stream in Melbourne, Australia, using two complementary approaches. Using a rapid bioassessment approach, indices of stream condition were calculated based on macroinvertebrate field surveys. Urban stream reaches supported impoverished macroinvertebrate communities, and contained potentially toxic concentrations of heavy metals and hydrocarbons. Using a field microcosm approach, a bioassay was carried out to assess sediment pollution effects on native macroinvertebrates. Sediment from urban sites substantially altered the microcosm macroinvertebrate community, most likely due to elevated heavy metal and hydrocarbon concentrations. Macroinvertebrate surveys combined with a bioassay approach based on field microcosms can help isolate the effect of stream pollutants in degraded ecosystems.     

Temporal variability of mercury speciation in urban air

Semi-continuous measurements of ambient mercury (Hg) species were performed in Detroit, MI, USA for the calendar year 2003. The mean (±standard deviation) concentrations for gaseous elemental mercury (GEM), particulate mercury (HgP), and reactive gaseous mercury (RGM) were 2.2±1.3 ng m⁻³, 20.8±30.0, and 17.7±28.9 pg m⁻³, respectively. A clear seasonality in Hg speciation was observed with GEM and RGM concentrations significantly (p<0.001) greater in warm seasons, while HgP concentrations were greater in cold seasons. The three measured Hg species also exhibited clear diurnal trends which were particularly evident during the summer months. Higher RGM concentrations were observed during the day than at night. Hourly HgP and GEM concentrations exhibited a similar diurnal pattern with both being inversely correlated with RGM. Multivariate analysis coupled with conditional probability function analysis revealed the conditions associated with high Hg concentration episodes, and identified the inter-correlations between speciated Hg concentrations, three common urban air pollutants (sulfur dioxide, ozone, and nitric oxides), and meteorological parameters. This analysis suggests that both local and regional sources were major factors contributing to the observed temporal variations in Hg speciation. Boundary layer dynamics and the seasonal meteorological conditions, including temperature and moisture content, were also important factors affecting Hg variability.     

Long-term mercury dynamics in UK soils

A model assuming first-order losses by evasion and leaching was used to evaluate Hg dynamics in UK soils since 1850. Temporal deposition patterns of Hg were constructed from literature information. Inverse modelling indicated that 30% of 898 rural sites receive Hg only from the global circulation, while in 51% of cases local deposition exceeds global. Average estimated deposition is 16 μg Hg m⁻² a⁻¹ to rural soils, 19 μg Hg m⁻² a⁻¹ to rural and non-rural soils combined. UK soils currently hold 2490 tonnes of reactive Hg, of which 2140 tonnes are due to anthropogenic deposition, mostly local in origin. Topsoil currently releases 5.1 tonnes of Hg⁰ per annum to the atmosphere, about 50% more than the anthropogenic flux. Sorptive retention of Hg in the lower soil exerts a strong control on surface water Hg concentrations. Following decreases in inputs, soil Hg concentrations are predicted to decline over hundreds of years.     

Cadmium speciation and accumulation in periphyton in a small stream with dynamic concentration variations

Accumulation of cadmium in periphyton was investigated under field conditions while Cd concentration and speciation were dynamically varying in a small stream during rain events. Speciation in water was determined in situ by diffusion gradient in thin-films (DGT) and by modeling of complexation with fulvic acids. During the rain events, dissolved Cd concentrations increased from 0.17 nM to 0.27-0.36 nM, and 70-97% were DGT-labile. Cd content in periphyton closely followed Cd concentrations in water, despite higher concentrations of Zn and Mn, and may be controlled by either free or DGT-labile Cd concentrations. Decrease of Cd content in periphyton after the rain events was slower than the decrease of Cd concentration in water. Concentrations of Zn, Mn, Cu, Pb and Fe in periphyton also followed the dynamic variations of metal concentrations in water. Repeated exposure of periphyton to elevated dissolved Cd may lead to Cd accumulation.     

Seasonal variation in dissolved gaseous mercury and total mercury concentrations in Juam Reservoir, Korea

Dissolved gaseous mercury (DGM) and total mercury (TM) concentrations were measured in Juam Reservoir, Korea. DGM concentrations were higher in spring (64+/-13pgL(-1)) and summer (109+/-15pgL(-1)), and lower in fall (20+/-2pgL(-1)) and winter (23+/-6pgL(-1)). In contrast, TM concentrations were higher in fall (3.2+/-0.1ngL(-1)) and winter (3.3+/-0.1ngL(-1)) than in spring (2.3+/-0.1ngL(-1)) and summer (2.2+/-0.4ngL(-1)). DGM concentrations were correlated with water temperature (p<0.0001), ORP (p<0.0001), UV intensity (UV-A: p=0.008; UV-B: p=0.003), and DOC concentration (p=0.0107). DGM concentrations varied diurnally with UV intensity. The average summer DGM (109+/-15pgL(-1)) and TM (2.2+/-0.4ngL(-1)) concentrations in Juam Reservoir were higher than the averages for North American lakes (DGM=38+/-16pgL(-1); TM=1.0+/-1.2ngL(-1)), but lower than levels reported for Baihua Reservoir in China.     

Periphyton as a bioindicator of mercury pollution in a temperate torrential river ecosystem

Mercury presents a potential risk to the environment and humans, especially in its methylated form. It is among the highest priority environmental pollutants. River Idrijca (Slovenia) is highly contaminated with mercury due to past mercury mining. The aim of this work was to investigate whether the periphyton community in rivers such as Idrijca is a suitable indicator of Hg pollution and of changes in mercury methylation and could serve as an early warning system of increased input of MeHg in the food chain. Periphyton is the only site of primary production in temperate torrential rivers such as Idrijca and is therefore an important link in the food chain. It is also a potential site of Hg accumulation and its introduction to higher trophic levels. Our aim was to assess the response of the periphyton to seasonal and spatial variations in mercury levels and to evaluate its potential as an early warning system of changes in mercury reactivity and mobilization The results indicate that periphyton in a torrential river is too complex and unpredictable to be used as a sole indicator of mercury concentrations and changes in the river. Nevertheless, it can complement environmental measurements due to its importance in the riverine food web.     

Mercury conversion processes in Amazon soils evaluated by thermodesorption analysis

This paper reports on the speciation study and the Hg redox behavior in Amazon soils not influenced by gold mining and collected near Manaus, AM, Brazil. The samples were incubated by adding Hg(0) and HgCl₂ to dry soil. Solid phase Hg speciation analysis was carried out using a Hg thermodesorption technique with the aim of distinguishing elemental Hg(0) from Hg(II) binding forms. In the first case, we observed the conversion of Hg(0) to Hg(II) binding forms in the range of 28–68% and a correlation between the percent of oxidation and OM content. Samples incubated with Hg(II) showed the formation of Hg(I) and/or Hg(0) in the range of 19–69%. The lowest values corresponded to the samples with the lowest clay contents. The kinetics of conversion of Hg(0) as well as HgCl₂ were roughly fitted to the two first order reactions, a fast one and a slow one. It was not possible to evaluate differences between sampling sites and types of soils, but the mean half-life of the first order reaction obtained by the addition of Hg(II) was slower (t_1/2 = 365 d) than the one obtained by the addition of Hg(0) (t_1/2 = 148 d). Previous studies have shown the predominance of organically bound Hg in these samples. Thus, the kinetic difference between Hg oxidation and reduction in combination with the efficient retention processes by OM may explain the high background values found in Amazon soils.     

Accumulation of mercury and methylmercury by mushrooms and earthworms from forest soils

Accumulation of total and methyl-Hg by mushrooms and earthworms was studied in thirty-four natural forest soils strongly varying in soil physico-chemical characteristics. Tissue Hg concentrations of both receptors did hardly correlate with Hg concentrations in soil. Both total and methyl-Hg concentrations in tissues were species-specific and dependent on the ecological groups of receptor. Methyl-Hg was low accounting for less than 5 and 8% of total Hg in tissues of mushrooms and earthworms, respectively, but with four times higher concentrations in earthworms than mushrooms. Total Hg concentrations in mushrooms averaged 0.96 mg Hg kg⁻¹ dw whereas litter decomposing mushrooms showed highest total Hg and methyl-Hg concentrations. Earthworms contained similar Hg concentrations (1.04 mg Hg kg⁻¹ dw) whereas endogeic earthworms accumulated highest amounts of Hg and methyl-Hg.     

Selenium speciation and localization in chironomids from lakes receiving treated metal mine effluent

A lake system in northern Saskatchewan receiving treated metal mine and mill effluent contains elevated levels of selenium (Se). An important step in the trophic transfer of Se is the bioaccumulation of Se by benthic invertebrates, especially primary consumers serving as a food source for higher trophic level organisms. Chironomids, ubiquitous components of many northern aquatic ecosystems, were sampled at lakes downstream of the milling operation and were found to contain Se concentrations ranging from 7 to 80 mg kg⁻¹ dry weight. For comparison, laboratory-reared Chironomus dilutus were exposed to waterborne selenate, selenite, or seleno-DL-methionine under laboratory conditions at the average total Se concentrations found in lakes near the operation. Similarities in Se localization and speciation in laboratory and field chironomids were observed using synchrotron-based X-ray fluorescence (XRF) imaging and X-ray absorption spectroscopy (XAS). Selenium localized primarily in the head capsule, brain, salivary glands and gut lining, with organic Se species modeled as selenocystine and selenomethionine being the most abundant. Similarities between field chironomids and C. dilutus exposed in the laboratory to waterborne selenomethionine suggest that selenomethionine-like species are most readily accumulated, whether from diet or water.     

Spatial and temporal variations of mercury levels in Okefenokee invertebrates: southeast Georgia

Accumulation of mercury in wetland ecosystems has raised concerns about impacts on wetland food webs. This study measured concentrations of mercury in invertebrates of the Okefenokee Swamp in Georgia, focusing on levels in amphipods, odonates, and crayfish. We collected and analyzed total mercury levels in these invertebrates from 32 sampling stations across commonly occurring sub-habitats. Sampling was conducted in December, May, and August over a two-year period. The highest levels of mercury were detected in amphipods, with total mercury levels often in excess of 20 ppm. Bioaccumulation pathways of mercury in invertebrates of the Okefenokee are probably complex; despite being larger and higher in the food chain, levels in odonates and crayfish were much lower than in amphipods. Mercury levels in invertebrates varied temporally with the highest levels detected in May. There was a lack of spatial variation in mercury levels which is consistent with aerial deposition of mercury.     

Estimating mercury emissions from a zinc smelter in relation to China’s mercury control policies

Mercury concentrations of flue gas at inlet/outlet of the flue gas cleaning, electrostatic demister, reclaiming tower, acid plant, and mercury contents in zinc concentrate and by-products were measured in a hydrometallurgical zinc smelter. The removal efficiency of flue gas cleaning, electrostatic demister, mercury reclaiming and acid plant was about 17.4%, 30.3%, 87.9% and 97.4% respectively. Flue gas cleaning and electrostatic demister captured 11.7% and 25.3% of the mercury in the zinc concentrate, respectively. The mercury reclaiming tower captured 58.3% of the mercury in the zinc concentrate. About 4.2% of the mercury in the zinc concentrate was captured by the acid plant. Consequently, only 0.8% of the mercury in the zinc concentrate was emitted to the atmosphere. The atmospheric mercury emission factor was 0.5 g t⁻¹ of zinc produced for the tested smelter, indicating that this process offers the potential to effectively reduce mercury emissions from zinc smelting.     

Changes in arsenic fractionation, bioaccessibility and speciation in organo-arsenical pesticide amended soils as a function of soil aging

Although organoarsenical pesticides are being phased out, sites with high concentrations of organic arsenical residues still exist due to the long-term application of these pesticides. The biotic and abiotic speciation of dimethylarsinic acid (DMA) can result in the formation of inorganic arsenic (As) species. Oxidation state, retention, and thereby persistence, varies according to temporal changes, influencing the availability and toxicity of contaminants. The current greenhouse study aimed at evaluating temporal changes in the oxidation state of As, geochemical partitioning, and bioaccessibility. Four soils with varying physiochemical properties were contaminated with DMA at two concentrations (675 and 1500 mg kg⁻¹ of As). Rice plants were grown for a 6 months period, following which, the soils were allowed to age. The operationally defined forms of As and its bioaccessibility was analyzed at 0, 6 months, 1 year, and 3 years. Changes in oxidation state of As were evaluated immediately after spiking and after 3 years of soil-pesticide equilibration. Results show that geochemical partitioning of As was affected significantly (P < 0.05) by soil type, loading rates, and equilibration time. Arsenic was bound mainly to the poorly-crystalline Fe/Al-oxyhydroxides in the soil. However, these interactions did not affect As bioaccessibility, presumably due to the dissolution of the bound fractions of As in the acidic stomach. While 74-94% of the total bioaccessible As was transformed to As(V), 4-19% was transformed to the more toxic As(III). This study indicates that although aging affected the geochemical partitioning of As in the soil, bioaccesibility was controlled by the gastric pH.