Investigation on elemental mercury removal by cerium modified semi-coke

Coal-fired power plant is the largest anthropogenic mercury source. Active carbon injection technique has been widely used to control the mercury emissions. However, high operation cost limits its development and it is necessary to find other potential mercury sorbents. In this study, raw semi-coke and a series of novel cerium (Ce) modified semi-cokes were synthesized and utilized for removing elemental mercury (Hg⁰) from simulated flue gas. It is noteworthy that the efficiencies were tested without hydrogen chloride (HCl) in order to evaluate the sorbents efficacy for low-chlorine (Cl) coal. The results show that the modified sorbents exhibited the best performance at 150 °C. The performance of sorbent could be reinforced due to the existence of oxygen (O₂), nitric oxide (NO) and HCl. The adverse effect caused by sulfur dioxide (SO₂) reduced dramatically after Ce modification. The negative impact of ammonia (NH₃) on Hg⁰ removal in this study could be neglected owing to the tiny concentration of NH₃. Raw semi-coke provided sufficient carbon content, which is favorable to mercury adsorption. As Ce loading increased, the carbon structure changed and the crystal of cerium oxide was formed in the modified semi-coke. The mass fraction of cerium oxide on the sorbent was over 4.4% when the concentration of Ce modification solution was higher than 0.2 mol L⁻¹. The redox reaction activity and the oxygen storage ability of Ce³⁺/Ce⁴⁺ gave a huge boost to the performance of modified semi-coke. The addition of Ce also had an impact on the proportion of oxygen species.     

Waste-to-wealth approach in water economy: The case of beneficiation of mercury-contaminated water in hydrogen production

Heavy metals (Hg, Cd, Pb, etc.) are micro-pollutants and result in water contamination. Significant bio-concentration of heavy metal like Hg can lead to fatal disease such as Minamata. Given this context, heavy metal removal from wastewater is essential before discharge. The wastewater treatment process requires considerable amount of energy which is being met by the conventional carbon-based fuels. This contributes to the global carbon dioxide emission, and hence global warming. Therefore, if clean energy sourcing is enabled during the treatment of the wastewater; it would offer obvious advantages. If the energy production is ‘clean’ and achieved via the process itself, it would serve two outcomes: (a) meeting the energy demand for wastewater treatment, and (b) getting rid of the need for external ‘carbon-based’ energy. Recently a few research articles have reported simultaneous clean energy production from wastewater during its treatment. Thus, the energy demand of the wastewater treatment process can be potentially met with the clean energy produced during the process. In this review, we will discuss mercury-contaminated wastewater treatment with simultaneous hydrogen production. We will provide a brief overview of waste-to-wealth approaches currently prevailing in water economy, recent mercury removal processes, and discuss future possibilities of self-sustained Hg-contaminated wastewater treatment.     

2016~2018年甘肃省市售蔬菜中铅汞污染状况及人体健康风险分析

目的 对甘肃省14个市州蔬菜中铅汞进行三年的采样监测,掌握铅汞重金属污染的基本情况并对人体健康风险进行了分析。方法 在全省14个市州共采集样品1213份,依据国标方法进行铅汞含量的测定,采用尼梅罗综合污染指数法对蔬菜中铅和汞污染程度进行评价,用目标危害指数法(THQ)和危害指数(HI)评价蔬菜中铅汞对成人和儿童的健康风险。结果 各类蔬菜中均检出了铅和汞,其中鳞茎类中的铅和茎类蔬菜中的汞检出率均达到了100%；块根和块茎类蔬菜铅的超标率为3.76%；汞含量除在茎类蔬菜中超标率为1.34%外,在其余种类中均未有超标。从铅汞的综合污染指数来看,除茎类蔬菜以外,其他都表现为Pb＞Hg,铅对蔬菜重金属污染贡献较大,其中瓜菜类和鳞茎类的铅含量综合污染指数分别为0.61和0.52,属于轻度污染；茄果类和块根块茎类蔬菜的铅含量综合污染指数分别达到了4.68和4.40,污染较严重。居民通过蔬菜摄入的铅汞的暴露风险儿童高于成人,但THQ和HI均小于1,对人体健康造成的影响不明显。结论 本次研究中甘肃省市售蔬菜中少数受到重金属铅的污染,其余蔬菜中铅汞含量对健康影响均在安全范围内。     

Mercury concentrations in commercial fish species from Lake Winnipeg, 1971–2019

Concentrations of total mercury (THg) in the axial musculature of northern pike (Esox lucius), walleye (Sander vitreus), lake whitefish (Coregonus clupeaformis), and sauger (Sander canadensis) were analyzed from several regions of Lake Winnipeg and three main inflows, focusing on Mossy Bay in the North Basin of the lake. Length-standardized means (standard means) indicated THg concentrations in pike of 550 mm fork length (0.44 ppm) and walleye measuring 400 mm (0.38 ppm) from Mossy Bay were highest in 1971 and declined to 0.13 and 0.22 ppm, respectively, by 1974. Standard means of both these species have been similar since 2010 (walleye; approximately 0.11 ppm) and 2013 (pike; approximately 0.17 ppm), except for a significant increase to 0.15 ppm in walleye in 2019, potentially related to concurrent changes in trophic interactions with invasive fish and invertebrate species. Standard means of 300 mm long sauger (0.23–0.29 ppm) did not decline significantly between 1971 and 1974, and those of 350 mm long whitefish ranged from 0.006 to 0.028 ppm from 1983 to 2016 with no clear temporal trend. In concert with data from other areas of Lake Winnipeg and the three inflows for 2000–2019, these results indicate higher contemporary concentrations in the South Basin of the lake. This latitudinal gradient in fish THg is assumed to be a result of continuous mercury inputs from the Red and the Winnipeg River, whereas a former point source of industrial mercury in the Saskatchewan River is no longer relevant. According to human consumption limits based on tolerable daily intake calculations and current THg concentrations of fish from Mossy Bay, substantial quantities of whitefish, pike, and walleye fish can be safely eaten.     

Mercury(II)-complex with 5-methyl-1,3,4-thiadiazole-2-thiol: kinetic studies of hydrogen storage

Mixed ligand mercury(II) complexes of 2-meracpto-5-methyl-1,3,4-thiazdiazole (HmtzS) and phosphines or diamines having the general formulae [Hg(mtsZ)₂(diphos)] {diphos = 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,4-bis(diphenylphosphino)butane (dppe), 1,1′-bis(diphenylphosphino)ferrocene (dppf)}, [Hg(mtsZ)₂(PPh₃)₂] and [Hg(mtsZ)₂(diamine)] {diamine = bipyridyl (Bipy) or 1,10-phenthroline (Phen), were successfully synthesized by simple mixing method. The complexes were characterized by elemental analysis, molar conductivity, IR and NMR (¹H, ¹³C and ³¹P) spectroscopic methods. The mtzS^? ligand was coordinated through the sulfur atom of thiol group, whereas the diphosphine or diamine ligands bonded as bidentate chelating ligand to afford tetrahedral environment around the Hg(II) ions. Moreover, the complex [Hg(mtsZ)₂] was used in order to study its ability to store hydrogen. The results of hydrogen isotherm at different temperatures prove that [Hg(mtsZ)₂] was able to store 0.8 wt% at a pressure of 80 bar 77 K. Furthermore, the kinetic study of hydrogen storage was studied and the kinetic study was carried out using the Langmuir. Moreover, the adsorption kinetic results revealed that hydrogen storage in [Hg(mtsZ)₂] follow the pseudo-second-order model with coefficient regression equal to 0.99.     

Comparison of chlorine and chloramine in the release of mercury from dental amalgam

The purpose of this project was to compare the ability of chlorine (HOCl/OCl⁻) and monochloramine (NH₂Cl) to mobilize mercury from dental amalgam. Two types of amalgam were used in this investigation: laboratory-prepared amalgam and samples obtained from dental-unit wastewater. For disinfectant exposure simulations, 0.5 g of either the laboratory-generated or clinically obtained amalgam waste was added to 250 mL amber bottles. The amalgam samples were agitated by end-over-end rotation at 30 rpm in the presence of 1 mg/L chlorine, 10 mg/L chlorine, 1 mg/L monochloramine, 10 mg/L monochloramine, or deionized water for intervals of 0 h, 2 h, 4 h, 8 h, and 24 h for the clinically obtained amalgam waste samples and 4 h and 24 h for the laboratory-prepared samples. Chlorine and monochloramine concentrations were measured with a spectrophotometer. Samples were filtered through a 0.45 µm membrane filter and analyzed for mercury with USEPA standard method 245.7. When the two sample types were combined, the mean mercury level in the 1 mg/L chlorine group was 0.020 mg/L (n = 25, SD = 0.008). The 10 mg/L chlorine group had a mean mercury concentration of 0.59 mg/L (n = 25, SD = 1.06). The 1 mg/L chloramine group had a mean mercury level of 0.023 mg/L (n = 25, SD = 0.010). The 10 mg/L chloramine group had a mean mercury level of 0.024 mg/L (n = 25, SD = 0.011). Independent samples t-tests showed that there was a significant difference between the natural log mercury measurements of 10 mg/L chlorine compared to those of 1 mg/L and 10 mg/L chloramine. Changing from chlorine to chloramine disinfection at water treatment plants would not be expected to produce substantial increases in dissolved mercury levels in dental-unit wastewater.     

Ecosystem matters: fish consumption, mercury intake and exposure among fluvial lake fish-eaters

Many studies use the number of fish meals as an estimate of Hg intake, although fish Hg concentrations, even within the same species, can greatly vary. Furthermore, most freshwater advisories only refer to local catch, while market fish advisories only focus on market fish, although both can contribute to Hg body burden. The present study, carried out in lakeside communities from 2 ecosystems in Quebec, Canada, sought to (i) estimate Hg intake from local freshwater sources, hunted waterfowl and market fish and seafood, and (ii) examine the relations between fish consumption, estimated Hg intake and biomarkers of exposure. A total of 238 adults (18-74 years), who had consumed local catch within the past three months, responded to an extensive interview-administered fish and waterfowl frequency questionnaire. Anthropometric measures were taken and a self-administered questionnaire was used to obtain socio-demographic information. Hg intake was estimated as µg Hg/kg body weight/day. Blood and hair samples were analyzed for Hg content. Results showed that persons from one ecosystem ate significantly more fish compared to those from the other (median: 52.1 g/day vs 38.9 g/day), but presented significantly lower concentrations of hair Hg (median: 448.0 ng/g vs 730.5 ng/g), blood organic Hg (median: 1.1 µg/L vs 3.4 µg/L) and inorganic Hg (median: 0.4 µg/L vs 0.8 µg/L). Median daily total Hg intake was 0.080 µg/kg bw/day for the former community and 0.141 µg/kg bw/day for the latter. Overall, 59.5% from the first ecosystem and 41.0% from the other, exceeded the US EPA RfD (0.1 µg/kg bw/day), while 13.2% and 6.0%, respectively, exceeded the Canadian tolerable daily intake (0.47 µg/kg bw/day) for adults. For the two groups, freshwater fish consumption frequency, but not total fish, was positively associated with bioindicators of Hg while estimated Hg intake from freshwater catch as well as from total fish consumption were positively related to Hg biomarkers. There was a positive relation between consumption and estimated Hg intake from freshwater fish and blood inorganic Hg. These findings indicate that the number of fish can be a poor surrogate for Hg exposure. The differences observed here for Hg intake and exposure reflect ecosystem disparities in fish diversity and Hg bioaccumulation. Studies and advisories need to consider Hg fish concentrations and fish-eating patterns in different ecosystems, as well as the contribution of market fish. The relation between fish consumption and inorganic Hg exposure, reported as well in other studies, needs to be further investigated.     

Mercury contamination in fish from gold mining areas in Indonesia and human health risk assessment

This study investigates the effects on fish and assesses human health hazards from mercury released in two gold mining areas in Indonesia: Tatelu (North Sulawesi Province) and Galangan (Katingan District, Central Kalimatan Province). In Tatelu, 154 fish specimens of 10 freshwater species were collected, as well as five marine species from the fish market. The mean concentration of total mercury in muscles of freshwater fish from this area was 0.58+/-0.44 microg/g, with more than 45% of fish having Hg levels above the WHO guideline for human consumption of 0.5 microg/g. In Galangan, where 263 fish specimens of 25 species were collected, the total mercury in muscles averaged 0.25+/-0.69 microg/g. Excluding data from flooded open pits in sub-area P4, mean Hg levels in fish from Galangan were 2 to 4 times lower than 0.5 microg/g, while fewer than 10% of fish from Galangan exceeded WHO guidelines. The Hazard Quotient (HQ) was applied to both areas to determine the threat of MeHg exposure for communities in both areas. The HQ is a risk assessment indicator which defines the ratio of exposure level to a single substance in relation to a reference dose. Samples from Tatelu (excluding marine species) had an HQ above one, while those from Galangan resulted in values of 2.4 for the whole area and 9.9 for sub-area P4, pointing to potentially harmful fish consumption for the local population. By using the single-compartment model to estimate mercury levels in blood and hair from daily intake dose, sub-area P4 showed the highest levels, higher than the upper limit guideline for pregnant women, but still lower than threshold levels associated with observed clinical effects.     

Urinary mercury in people living near point sources of mercury emissions

As part of the European Mercury Emissions from Chlor Alkali Plants (EMECAP) project, we tested the hypothesis that contamination of ambient air with mercury around chlor alkali plants using mercury cells would increase the internal dose of mercury in people living close to the plants. Mercury in urine (U-Hg) was determined in 225 individuals living near a Swedish or an Italian chlor alkali plant, and in 256 age- and sex-matched individuals from two reference areas. Other factors possibly affecting mercury exposure were examined. Emissions and concentrations of total gaseous mercury (TGM) around the plants were measured and modeled. No increase in U-Hg could be demonstrated in the populations living close to the plants. This was the case also when the comparison was restricted to subjects with no dental amalgam and low fish consumption. The emissions of mercury to air doubled the background level, but contributed only about 2 ng/m(3) to long-term averages in the residential areas. The median U-Hg levels in subjects with dental amalgam were 1.2 microg/g creatinine (micro/gC) in Italy and 0.6 microg/gC in Sweden. In individuals without dental amalgam, the medians were 0.9 microg/gC and 0.2 microg/gC, respectively. The number of amalgam fillings, as well as chewing, fish consumption, and female sex were associated with higher U-Hg. The difference between the countries is probably due to higher fish consumption in Italy, demethylated methyl mercury (MeHg) being partly excreted in urine. Post hoc power calculations showed that if the background mercury exposure is low it may be possible to demonstrate an increase in U-Hg of as little as about 10 ng/m(3) as a contribution to ambient mercury from a point source.     

Heavy metal exposure in patients suffering from electromagnetic hypersensitivity

Background

Risks from electromagnetic devices are of considerable concern. Electrohypersensitive (EHS) persons attribute a variety of rather unspecific symptoms to the exposure to electromagnetic fields. The pathophysiology of EHS is unknown and therapy remains a challenge.

Objectives

Heavy metal load has been discussed as a potential factor in the symptomatology of EHS patients. The main objective of the study was to test the hypothesis of a link between EHS and heavy metal exposure.

Methods

We measured lead, mercury and cadmium concentrations in the blood of 132 patients (n = 42 males and n = 90 females) and 101 controls (n = 34 males and n = 67 females).

Results

Our results show that heavy metal load is of no concern in most cases of EHS but might play a role in exceptional cases.

Conclusions

The data do not support the general advice to heavy metal detoxification in EHS.