The influence of mariculture on mercury distribution in sediments and fish around Hong Kong and adjacent mainland China waters

To study the influence of mariculture on mercury (Hg) speciation and distribution in sediments and cultured fish around Hong Kong and adjacent mainland China waters, sediment samples were collected from six mariculture sites and the corresponding reference sites, 200-300 m away from the mariculture sites. Mariculture activities increased total mercury, organic matter, carbon, nitrogen and sulfur concentrations in the surface sediments underneath mariculture sites, possibly due to the accumulation of unconsumed fish feed and fish excretion. However, methylmercury (MeHg) concentrations and the ratio of MeHg to THg (% MeHg) in sediments underneath mariculture sites were lower than the corresponding reference sites. The % MeHg in sediments was negatively correlated (r = −0.579, p < 0.05) with organic matter (OM) content among all sites, indicating that OM may have inhibited Hg methylation in surface sediments. Three mariculture fish species were collected from each mariculture site, including red snapper (Lutjanus campechanus), orange-spotted grouper (Epinephelus coioides) and snubnose pompano (Trachinotus blochii). The average MeHg concentration in fish muscle was 75 μg kg⁻¹ (wet weight), and the dietary intake of MeHg through fish consumption for Hong Kong residents was 0.37 μg kg⁻¹ week⁻¹, which was lower than the corresponding WHO limits (500 μg kg⁻¹ and 1.6 μg kg⁻¹ week⁻¹).     

Characterization of mercury species in brown and white rice (Oryza sativa L.) grown in water-saving paddies

In China, total Hg (Hg_T) and methylmercury (MeHg) were quantified in rice grain grown in three sites using water-saving rice cultivation methods, and in one Hg-contaminated site, where rice was grown under flooded conditions. Polished white rice concentrations of Hg_T (water-saving: 3.3 ± 1.6 ng/g; flooded: 110 ± 9.2 ng/g) and MeHg (water-saving 1.3 ± 0.56 ng/g; flooded: 12 ± 2.4 ng/g) were positively correlated with root-soil Hg_T and MeHg contents (Hg_T: r² = 0.97, MeHg: r² = 0.87, p < 0.05 for both), which suggested a portion of Hg species in rice grain was derived from the soil, and translocation of Hg species from soil to rice grain was independent of irrigation practices and Hg levels, although other factors may be important. Concentrations of Hg_T and other trace elements were significantly higher in unmilled brown rice (p < 0.05), while MeHg content was similar (p > 0.20), indicating MeHg infiltrated the endosperm (i.e., white rice) more efficiently than inorganic Hg(II).     

Mercury accumulation in marine bivalves: influences of biodynamics and feeding niche

Differences in the accumulation of mercury (Hg) in five species of marine bivalves, including scallops Chlamys nobilis, clams Ruditapes philippinarum, oysters Saccostrea cucullata, green mussels Perna viridis, and black mussels Septifer virgatus, were investigated. The bivalves displayed different patterns of Hg accumulation in terms of the body concentrations of methylmercury (MeHg) and total Hg (THg), as well as the ratio of MeHg to THg. Parameters of the biodynamics of the accumulation of Hg(II) and MeHg could reflect the species-dependent Hg concentrations in the bivalves. With the exception of black mussels, we found a significant relationship between the efflux rates of Hg(II) and the THg concentrations in the bivalves. The interspecific variations in the MeHg to THg ratio were largely controlled by the relative difference between the elimination rates of Hg(II) and MeHg. Stable isotope (δ¹³C) analysis indicated that the five bivalve species had contrasting feeding niches, which may also affect the Hg accumulation.     

A laboratory-incubated redox oscillation experiment to investigate Hg fluxes from highly contaminated coastal marine sediments (Gulf of Trieste,Northern Adriatic Sea)

Mercury (Hg) mobility at the sediment–water interface was investigated during a laboratory incubation experiment conducted with highly contaminated sediments (13 μg g^-1) of the Gulf of Trieste. Undisturbed sediment was collected in front of the Isonzo River mouth, which inflows Hg-rich suspended material originating from the Idrija (NW Slovenia) mining district. Since hypoxic and anoxic conditions at the bottom are frequently observed and can influence the Hg biogeochemical behavior, a redox oscillation was simulated in the laboratory, at in situ temperature, using a dark flux chamber. Temporal variations of several parameters were monitored simultaneously: dissolved Hg (DHg) and methylmercury (MeHg), O₂, NH₄ ⁺, NO₃ ^- + NO₂ ^-, PO₄ ^3-, H₂S, dissolved Mn²⁺, dissolved inorganic and organic carbon (DIC and DOC). Under anoxic conditions, both Hg (665 ng m² day^-1) and MeHg (550 ng m² day^-1) fluxed from sediments into the water column, whereas re-oxygenation caused concentrations of MeHg and Hg to rapidly drop, probably due to re-adsorption onto Fe/Mn-oxyhydroxides and enhanced demethylation processes. Hence, during anoxic events, sediments of the Gulf of Trieste may be considered as an important source of DHg species for the water column. On the contrary, re-oxygenation of the bottom compartment mitigates Hg and MeHg release from the sediment, thus acting as a natural “defence” from possible interaction between the metal and the aquatic organisms.     

Mercury in San Francisco Bay forage fish

In the San Francisco Estuary, management actions including tidal marsh restoration could change fish mercury (Hg) concentrations. From 2005 to 2007, small forage fish were collected and analyzed to identify spatial and interannual variation in biotic methylmercury (MeHg) exposure. The average whole body total Hg concentration was 0.052 μg g⁻¹ (wet-weight) for 457 composite samples representing 13 fish species. MeHg constituted 94% of total Hg. At a given length, Hg concentrations were higher in nearshore mudflat and wetland species (Clevelandia ios, Menidia audens, and Ilypnus gilberti), compared to species that move offshore (e.g., Atherinops affinis and Lepidogobius lepidus). Gut content analysis indicated similar diets between Atherinops affinis and Menidia audens, when sampled at the same locations. Hg concentrations were higher in sites closest to the Guadalupe River, which drains a watershed impacted by historic Hg mining. Results demonstrate that despite differences among years and fish species, nearshore forage fish exhibit consistent Hg spatial gradients.     

Mercury exposure in the freshwater tilapia Oreochromis niloticus

Mercury (Hg) can be strongly accumulated and biomagnified along aquatic food chain, but the exposure pathway remains little studied. In this study, we quantified the uptake and elimination of both inorganic mercury [as Hg(II)] and methylmercury (as MeHg) in an important farmed freshwater fish, the tilapia Oreochromis niloticus, using ²⁰³Hg radiotracer technique. The dissolved uptake rates of both mercury species increased linearly with Hg concentration (tested at ng/L levels), and the uptake rate constant of MeHg was 4 times higher than that of Hg(II). Dissolved uptake of mercury was highly dependent on the water pH and dissolved organic carbon concentration. The dietborne assimilation efficiency of MeHg was 3.7-7.2 times higher than that of Hg(II), while the efflux rate constant of MeHg was 7.1 times lower. The biokinetic modeling results showed that MeHg was the greater contributor to the overall mercury bioaccumulation and dietary exposure was the predominant pathway.     

Selenium,total mercury and methylmercury in sardine: Study of molar ratio and protective effect on the diet

The purpose of this work was to evaluate the risk-benefit associated with canned sardine consumption, considering the selenium, the mercury and the methylmercury contents and the Se:Hg molar ratio and the Se-health benefit value (HBV) index. In this study, 63 canned sardine samples were purchased worldwide and for the determination of selenium and mercury species, the inductively coupled plasma optical emission spectrometry and thermal decomposition and amalgamation atomic absorption spectrometry were employed. The mean results obtained for the Brazilian samples varied between 12.6 and 65.5?μg kg^?1 for Hg; <3.7 and 45.4?μg kg^?1 for methylmercury; 310 and 1370?μg kg^?1 for Se. The MeHg/Hg ratio showed that the most toxic forms of Hg (MeHg) is predominant in 52 and 39% of the Brazilian samples conserved in tomato sauce and in oil, respectively. Nevertheless, the Se-HBV index and the Hg:Se and Se:Hg molar ratios indicated that the selenium content in canned sardine samples is enough to provide a protective effect on the Hg species.     

Mercury mass balance study in Wujiangdu and Dongfeng Reservoirs, Guizhou, China

From October 2003 to September 2004, we conducted a detailed study on the mass balance of total mercury (THg) and methylmercury (MeHg) of Dongfeng (DF) and Wujiangdu (WJD) reservoirs, which were constructed in 1992 and 1979, respectively. Both reservoirs were net sinks for THg on an annual scale, absorbing 3319.5 g km⁻² for DF Reservoir, and 489.2 g km⁻² for WJD Reservoirs, respectively. However, both reservoirs were net sources of MeHg to the downstream ecosystems. DF Reservoir provided a source of 32.9 g MeHg km⁻² yr⁻¹, yielding 10.3% of the amount of MeHg that entered the reservoir, and WJD Reservoir provided 140.9 g MeHg km⁻² yr⁻¹, yielding 82.5% of MeHg inputs. Our results implied that water residence time is an important variable affecting Hg methylation rate in the reservoirs. Our study shows that building a series of reservoirs in line along a river changes the riverine system into a natural Hg methylation factory which markedly increases the %MeHg in the downstream reservoirs; in effect magnifying the MeHg buildup problem in reservoirs.     

Total and Methylmercury in Soft Tissues of White-Tailed Eagle (Haliaeetus albicilla) and Osprey (Pandion haliaetus) Collected in Poland

Mercury (Hg) contamination in piscivorous birds, especially methylmercury (MeHg), has been drawing much attention worldwide in regard to its bioaccumulation and biomagnification in food chains. In this study on Hg in the soft tissues of white-tailed eagles (n = 22) and ospreys (n = 2) from Poland, total Hg (THg) range was 0.15–47.6 while MeHg range was 0.11–8.05 mg kg⁻¹ dry weight. In both species, median THg and MeHg concentrations were lower in the muscle and brain than in the liver and kidney. Median nephric residues were just under 3 and 5 mgTHg kg⁻¹ or 0.9 and 3.7 mgMeHg kg⁻¹ for white-tailed eagle and osprey, respectively. In Norwegian data from the 1970s and in our results, MeHg in the muscle of white-tailed eagle was ~60 % THg (%MeHg = MeHg/THg × 100), lower than in other piscivorous birds. A clear similarity in THg tissue levels was found between Polish and German populations of white-tailed eagles.     

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.     

Potential sources of methylmercury in tree foliage

Litterfall is a major source of mercury (Hg) and toxic methylmercury (MeHg) to forest soils and influences exposures of wildlife in terrestrial and aquatic ecosystems. However, the origin of MeHg associated with tree foliage is largely unknown. We tested the hypothesis that leaf MeHg is influenced by root uptake and thereby related to MeHg levels in soils. Concentrations of MeHg and total Hg in deciduous and coniferous foliage were unrelated to those in soil at 30 urban and rural forested locations in southwest Ohio. In contrast, tree genera and trunk diameter were significant variables influencing Hg in leaves. The fraction of total Hg as MeHg averaged 0.4% and did not differ among tree genera. Given that uptake of atmospheric Hg(0) appears to be the dominant source of total Hg in foliage, we infer that MeHg is formed by in vivo transformation of Hg in proportion to the amount accumulated.     

Importance of sulfate reducing bacteria in mercury methylation and demethylation in periphyton from Bolivian Amazon region

Sulfate reducing bacteria (SRB) are important mercury methylators in sediments, but information on mercury methylators in other compartments is ambiguous. To investigate SRB involvement in methylation in Amazonian periphyton, the relationship between Hg methylation potential and SRB (Desulfobacteraceae, Desulfobulbaceae and Desulfovibrionaceae) abundance in Eichhornia crassipes and Polygonum densiflorum root associated periphyton was examined. Periphyton subsamples of each macrophyte were amended with electron donors (lactate, acetate and propionate) or inhibitors (molybdate) of sulfate reduction to create differences in SRB subgroup abundance, which was measured by quantitative real-time PCR with primers specific for the 16S rRNA gene. Mercury methylation and demethylation potentials were determined by a stable isotope tracer technique using ²⁰⁰HgCl and CH₃²⁰²HgCl, respectively. Relative abundance of Desulfobacteraceae (<0.01-12.5%) and Desulfovibrionaceae (0.01-6.8%) were both highly variable among samples and subsamples, but a significant linear relationship (p < 0.05) was found between Desulfobacteraceae abundance and net methylmercury formation among treatments of the same macrophyte periphyton and among all P. densiflorum samples, suggesting that Desulfobacteraceae bacteria are the most important mercury methylators among SRB families. Yet, molybdate only partially inhibited mercury methylation potentials, suggesting the involvement of other microorganisms as well. The response of net methylmercury production to the different electron donors and molybdate was highly variable (3-1104 pg g⁻¹ in 12 h) among samples, as was the net formation in control samples (17-164 pg g⁻¹ in 12 h). This demonstrates the importance of community variability and complexity of microbial interactions for the overall methylmercury production in periphyton and their response to external stimulus.     

Net methylmercury production as a basis for improved risk assessment of mercury-contaminated sediments

Sediments contaminated by various sources of mercury (Hg) were studied at 8 sites in Sweden covering wide ranges of climate, salinity, and sediment types. At all sites, biota (plankton, sediment living organisms, and fish) showed enhanced concentrations of Hg relative to corresponding organisms at nearby reference sites. The key process determining the risk at these sites is the net transformation of inorganic Hg to the highly toxic and bioavailable methylmercury (MeHg). Accordingly, Hg concentrations in Perca fluviatilis were more strongly correlated to MeHg (p < 0.05) than to inorganic Hg concentrations in the sediments. At all sites, except one, concentrations of inorganic Hg (2-55 microg g(-1)) in sediments were significantly, positively correlated to the concentration of MeHg (4-90 ng g(-1)). The MeHg/Hg ratio (which is assumed to reflect the net production of MeHg normalized to the Hg concentration) varied widely among sites. The highest MeHg/Hg ratios were encountered in loose-fiber sediments situated in southern freshwaters, and the lowest ratios were found in brackish-water sediments and firm, minerogenic sediments at the northernmost freshwater site. This pattern may be explained by an increased MeHg production by methylating bacteria with increasing temperature, availability of energy-rich organic matter (which is correlated with primary production), and availability of neutral Hg sulfides in the sediment pore waters. These factors therefore need to be considered when the risk associated with Hg-contaminated sediments is assessed.     

Effects of land use conversion and fertilization on CH<Subscript>4</Subscript> and N<Subscript>2</Subscript>O fluxes from typical hilly red soil

Land use conversion and fertilization have been widely reported to be important managements affecting the exchanges of greenhouse gases between soil and atmosphere. For comprehensive assessment of methane (CH₄) and nitrous oxide (N₂O) fluxes from hilly red soil induced by land use conversion and fertilization, a 14-month continuous field measurement was conducted on the newly converted citrus orchard plots with fertilization (OF) and without fertilization (ONF) and the conventional paddy plots with fertilization (PF) and without fertilization (PNF). Our results showed that land use conversion from paddy to orchard reduced the CH₄ fluxes at the expense of increasing the N₂O fluxes. Furthermore, fertilization significantly decreased the CH₄ fluxes from paddy soils in the second stage after conversion, but it failed to affect the CH₄ fluxes from orchard soils, whereas fertilizer applied to orchard and paddy increased soil N₂O emissions by 68 and 113.9 %, respectively. Thus, cumulative CH₄ emissions from the OF were 100 % lower, and N₂O emissions were 421 % higher than those from the PF. Although cumulative N₂O emissions were stimulated in the newly converted orchard, the strong reduction of CH₄ led to lower global warming potentials (GWPs) as compared to the paddy. Besides, fertilization in orchard increased GWPs but decreased GWPs of paddy soils. In addition, measurement of soil moisture, temperature, dissolved carbon contents (DOCs), and ammonia (NH₄ ⁺-N) and nitrate (NO₃ ^?-N) contents indicated a significant variation in soil properties and contributed to variations in soil CH₄ and N₂O fluxes. Results of this study suggest that land use conversion from paddy to orchard would benefit for reconciling greenhouse gas mitigation and citrus orchard cultivation would be a better agricultural system in the hilly red soils in terms of greenhouse gas emission. Moreover, selected fertilizer rate applied to paddy would lead to lower GWPs of CH₄ and N₂O. Nevertheless, more field measurements from newly converted orchard are highly needed to gain an insight into national and global accounting of CH₄ and N₂O emissions.     

Acidification of a solonetzic soil by nitrogenous fertilizers

Abstract

Annual applications of (NH₄)₂SO₄ NH₄NO₃ and urea on a Solonetzic soil at 112 kg N/ha for 10 consecutive years reduced pH levels from 5.6 for the check to 4.4, 4.9 and 5.3, respectively for (NH₄)₂SO₄, NH₄NO₃ and urea. (NH₄)₂SO₄ generated twice as much exchange acidity as NH₄NO₃ and four times as much as urea. Net extractable cations leached from the Ap horizon closely approximated the amount of exchange acidity generated by (NH₄)₂SO₄ and NH₄NO₃ fertilizers. The levels of soil extractable Al and Mn were greatly enhanced by (NH₄)₂SO₄ as were plant contents. Similar acidifying effects to that produced by the (NH₄)₂SO₄ occurred when NH₄NO₃ was applied at 300 kg N/ha annually for 12 consecutive years in another field experiment on the same soil. Liming samples of the field (NH₄)₂SO₄ acidified soils in the greenhouse, significantly increased yields and lowered the Al and Mn contents of the plants to normal levels.     

Spatial trend and pollution assessment of total mercury and methylmercury pollution in the Pearl River Delta soil, South China

Total mercury (THg) and methylmercury (MeHg) were measured in large number of soil samples collected from areas with different types of land use, different depth in the Pearl River Delta (PRD) of South China. THg and MeHg concentrations ranged from 16.7 to 3320 ng g⁻¹ and 0.01 to 1.34 ng g⁻¹, respectively. THg levels are highest in the top 0-20 cm soil layer, and decrease from the surface to bottom layer soil. Spatial variation was observed with different types of land use. Urban parks had the highest concentrations and the other areas tended to decrease in the order of residential areas, industrial areas, vegetable fields, cereal fields, and woodlands. Temporal variation was also noted, and two relatively high THg contamination zones located in the northwestern part of the PRD have significantly expanded over the last two decades. Both THg and MeHg concentrations were correlated significantly with soil organic matter (OM), but not with soil pH. THg pollution status was evaluated using two assessment methods.     

Atmospheric concentrations of ammonia and ammonium at an agricultural site in the southeast United States

In this study, we present ∼1 yr (October 1998–September 1999) of 12-hour mean ammonia (NH₃), ammonium (NH₄⁺), hydrochloric acid (HCl), chloride (Cl⁻), nitrate (NO₃⁻), nitric acid (HNO₃), nitrous acid (HONO), sulfate (SO₄²⁻), and sulfur dioxide (SO₂) concentrations measured at an agricultural site in North Carolina's Coastal Plain region. Mean gas concentrations were 0.46, 1.21, 0.54, 5.55, and 4.15 μg m⁻³ for HCl, HNO₃, HONO, NH₃, and SO₂, respectively. Mean aerosol concentrations were 1.44, 1.23, 0.08, and 3.37 μg m⁻³ for NH₄⁺, NO₃⁻, Cl⁻, and SO₄²⁻, respectively. Ammonia, NH₄⁺, HNO₃, and SO₄²⁻ exhibit higher concentrations during the summer, while higher SO₂ concentrations occur during winter. A meteorology-based multivariate regression model using temperature, wind speed, and wind direction explains 76% of the variation in 12-hour mean NH₃ concentrations (n=601). Ammonia concentration increases exponentially with temperature, which explains the majority of variation (54%) in 12-hour mean NH₃ concentrations. Dependence of NH₃ concentration on wind direction suggests a local source influence. Ammonia accounts for >70% of NH_x (NH_x=NH₃+NH₄⁺) during all seasons. Ammonium nitrate and sulfate aerosol formation does not appear to be NH₃ limited. Sulfate is primarily associated ammonium sulfate, rather than bisulfate, except during the winter when the ratio of NO₃⁻–NH₄⁺ is ∼0.66. The annual average NO₃⁻–NH₄⁺ ratio is ∼0.25.     

Wet deposition of mercury within the vicinity of a cement plant before and during cement plant maintenance

Hg species (total mercury, methylmercury, reactive mercury) in precipitation were investigated in the vicinity of the Lehigh Hanson Permanente Cement Plant in the San Francisco Bay Area, CA., USA. Precipitation was collected weekly between November 29, 2007 and March 20, 2008, which included the period in February and March 2008 when cement production was minimized during annual plant maintenance. When the cement plant was operational, the volume weighted mean (VWM) and wet depositional flux for total Hg (Hg_T) were 6.7 and 5.8 times higher, respectively, compared to a control site located 3.5 km east of the cement plant. In February and March, when cement plant operations were minimized, levels were approximately equal at both sites (the ratio for both parameters was 1.1). Due to the close proximity between the two sites, meteorological conditions (e.g., precipitation levels, wind direction) were similar, and therefore higher VWM Hg_T levels and Hg_T deposition likely reflected increased Hg emissions from the cement plant. Methylmercury (MeHg) and reactive Hg (Hg(II)) were also measured; compared to the control site, the VWM for MeHg was lower at the cement plant (the ratio = 0.75) and the VWM for Hg(II) was slightly higher (ratio = 1.2), which indicated the cement plant was not likely a significant source of these Hg species to the watershed.     

Concentrations of methylmercury in invertebrates from wetlands of the Prairie Pothole Region of North America

Prairie wetlands may be important sites of mercury (Hg) methylation resulting in elevated methylmercury (MeHg) concentrations in water, sediments and biota. Invertebrates are an important food resource and may act as an indicator of MeHg exposure to higher organisms. In 2007-2008, invertebrates were collected from wetland ponds in central Saskatchewan, categorized into functional feeding groups (FFGs) and analyzed for total Hg (THg) and MeHg. Methylmercury and THg concentrations in four FFGs ranged from 0.2-393.5 ng · g(-1) and 9.7-507.1 ng · g(-1), respectively. Methylmercury concentrations generally increased from gastropods with significantly lower average MeHg concentrations compared to other invertebrate taxa. Surrounding land use (agricultural, grassland and organic agricultural) may influence MeHg concentrations in invertebrates, with invertebrate MeHg concentrations being higher from organic ponds (457.5 ± 156.7 ng · g(-1)) compared to those from grassland ponds (74.8 ± 14.6 ng · g(-1)) and ponds on agricultural lands (32.8 ± 6.2 ng · g(-1)).