Relatório da Avaliação da Capacidade Institucional - Moçambique: maio de 2020: Testar um novo enquadramento da OMS para apoiar o desenvolvimento de estratégias de saúde pública no setor da extração de ouro artesanal e em pequena escala no contexto da Convenção de Minamata sobre o mercúrio / Institutional Capacity Assessment Report: Mozambique

O presente relatório apresenta uma avaliação da disponibilidade institucional para detetar, prevenir e abordar os problemas de saúde associados à ASGM, e assume o objetivo de prestar um contributo ao Ministério da Saúde (MISAU) na definição das prioridades no âmbito da Estratégia para a Saúde Pública sobre a ASGM. Com base na consulta de representantes do MISAU, bem como de vários outros ministérios e grupos de interessados na área da ASGM, o relatório avalia os pontos fortes das capacidades institucionais e os desafios para o setor da saúde pública, identificando os principais interessados relevantes para o desenvolvimento e implementação de uma estratégia de saúde pública para o setor da ASGM.

This report presents an assessment of the institutional readiness to detect, prevent and address health issues associated with ASGM and aims to provide an input to the Ministry of Health (MISAU) to define key priorities in the Public Health Strategy on ASGM. Based on the consultation of representatives of MISAU as well as various other ministries and stakeholder groups concerned with ASGM, the report assesses institutional capacity strengths and challenges in the public health sector and identifies key stakeholders relevant for the development and implementation of a public health strategy for the ASGM sector.

Dissolved Gaseous Mercury Production at a Marine Aquaculture Site in the Mercury-Contaminated Marano and Grado Lagoon, Italy.

Dissolved gaseous mercury (DGM) production was examined in relation to ultraviolet radiation within a marine aquaculture site in the contaminated Marano and Grado Lagoon (Italy). The measured rates of DGM production relative to time elapsed (17.06 and 20.68 pg h-1, respectively) were substantially (6-20 times) higher than what has been observed in other marine Hg studies. We measured similar levels of DGM relative to dissolved total mercury (THgD) (0.84%-8.91%) at these sites in comparison to uncontaminated marine sites, however relative to other moderately-contaminated marine sites in Portugal the % DGM/THgD was high. These results suggest a substantial capacity for Hg volatilization from these highly contaminated lagoons to the atmosphere due to photoreduction mechanisms.

Photoinduced reduction of high concentration Hg(II) to Hg2Cl2 from acid wastewater with the presence of fulvic acid under anaerobic conditions.

In order to recover mercury from high concentration Hg(II) acid wastewater, UV irradiation was used to reduce Hg(II) to Hg2Cl2 with the presence of fulvic acid and chloride ion. When simulated wastewater with Hg(II) concentration of 1000 mg L-1 was treated, > 90% of Hg(II) removal efficiency was achieved under the condition of extra Cl- dosage of 5 g L-1, FA dosage of 2 g L-1, pH of 3.0 and 120 min of UV irradiation. Kinetics study showed that the photoreduction process could be well described by pseudo-first order kinetic mode, and the Hg(II) reduction rate was tested to be 0.0422 min-1. Characterization results indicated that FA-Hg(II) complexes were firstly formed and then broken down into smaller molecules after the UV treatment, in which process highly reductive species (i.e. COO, COOH) were produced. These reductive species mediated the reduction of Hg(II). With the presence of Cl-, Hg2Cl2 was practically the only detected Hg-based product in the photoreduction process. This technique was also employed to treat CODCr analysis wastewater (initial Hg(II) concentration > 1000 mg L-1). With 90 min of reaction, most of the Hg(II) was removed from the system leaving less than 30% that could be further treated by chemical participation or adsorption method.

[Influence of light wavelength and intensity on the reduction of divalent mercury in aquatic system].

Laboratory experiments were conducted to investigate the photo-reduction of HgCI2, under various light wavelengths and intensities. The whole process was tracked by changing Hg0 concentrations in argon and Hg0 flux was calculated for qualitative and quantitative analysis; the rate order was determined by both differential and integral methods. The principal results indicated: Higher mercury emission flux was observed under shorter light wavelength and stronger intensity, which shows the important role of photoenergy in the reaction. The degree of mercury reduction was determined by radiation wavelength and intensity, and it was also influenced by solution volume and the flow rate of carrier gas. Under different light conditions, Hg0 concentrations in argon all increased at the beginning and decreased after a specific time period, since the main reactions in rising period were the photo-reduction of Hg2+ and the emission of Hg0 while the reaction in decreasing period was the emission of Hg0 only. The rate order under visible light was the first order while it was the second order under UVA and UVB, which attributes to the fact that coordination complex has certain light absorption band, which is related with the available light wavelength provided by experimental lamps.

Effect of Nd:YAG laser pulse energy on mercury vapor release from the dental amalgam.

OBJECTIVE: The aim of this study was to evaluate the effect of different pulse energies of Nd:YAG laser on the amalgam ablation, and its effect on the amount of mercury vapor release from amalgam. BACKGROUND DATA: Toxic vapor release from amalgam restorations at the laser focus site is possible. MATERIALS AND METHODS: Forty-five amalgam samples (4 mm in diameter and 5 mm in height) were placed in sealed containers and underwent Nd:YAG laser irradiation with pulse energies of 50, 150, and 250 mJ at a distance of 1 mm from the amalgam surface for 4 sec. Subsequently, 150 mL of air was collected from the inside of the container using an Apex Pump to analyze the amount of mercury vapor in the air samples using a mercury vapor analyzer. Data were analyzed using Kruskal-Wallis and Mann-Whitney U tests (p<0.05). RESULTS: The amount of mercury vapor release significantly increased with an increase in the pulse energy of Nd:YAG laser (p<0.001). In addition, the amount of mercury vapor release with 250 mJ pulse energy was significantly higher compared with the standard mercury vapor concentration (50 µg/m(3)) (p<0.001). Nd:YAG laser produced cavities on the amalgam surface, which increased in size with an increase in the energy of the laser beam. CONCLUSIONS: The amount of mercury vapor significantly increased with an increase in the pulse energy of the laser beam, and was significantly higher than the standard mercury vapor concentration with 250 mJ pulse energy.

Photocurrent characteristics of HgTe nanoparticle films-Si nanowires heterojunctions made using a simple transfer-dropping method.

In this study, pn heterojunction diodes are constructed with p-type HgTe nanoparticle (NP) films dropped by a nanoplotter and n-type Si nanowires (NWs) transferred onto plastic substrates and their optoelectronic characteristics are investigated under the illumination of 633-nm wavelength light. The rectification ratio when light is irradiated on the diode is twice that in the dark. The photocurrent efficiency of the diode at a bias voltage of 2.5 V is determined to be 0.41 microA/W, which is greater than that of the transferred Si NWs.

Electrospun metal oxide-TiO2 nanofibers for elemental mercury removal from flue gas.

Nanofibers prepared by an electrospinning method were used to remove elemental mercury (Hg(0)) from simulated coal combustion flue gas. The nanofibers composed of different metal oxides (MO(x)) including CuO, In(2)O(3), V(2)O(5), WO(3) and Ag(2)O supported on TiO(2) have been characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersing X-ray (EDX) and UV-vis spectra. The average diameters of these nanofibers were about 200nm. Compared to pure TiO(2), the UV-vis absorption intensity for MO(x)-TiO(2) increased significantly and the absorption bandwidth also expanded, especially for Ag(2)O-TiO(2) and V(2)O(5)-TiO(2). Hg(0) oxidation efficiencies over the MO(x)-TiO(2) nanofibers were tested under dark, visible light (vis) irradiation and UV irradiation, respectively. The results showed that WO(3) doped TiO(2) exhibited the highest Hg(0) removal efficiency of 100% under UV irradiation. Doping V(2)O(5) into TiO(2) enhanced Hg(0) removal efficiency greatly from 6% to 63% under visible light irradiation. Ag(2)O doped TiO(2) showed a steady Hg(0) removal efficiency of around 95% without any light due to the formation of silver amalgam. An extended experiment with 8 Hg(0) removal cycles showed that the MO(x)-TiO(2) nanofibers were stable for removing Hg(0) from flue gas. Factors responsible for the enhanced photocatalytic activities of the MO(x)-TiO(2) nanofibers were also discussed.

L-cysteine functionalized gold nanoparticles for the colorimetric detection of Hg2+ induced by ultraviolet light.

A simple, cost-effective yet rapid and sensitive colorimetric sensor for the detection of Hg(2+) using L-cysteine functionalized gold nanoparticles induced by ultraviolet radiation was developed. The sensitivity and selectivity of detection was also investigated. The L-cysteine modified gold nanoparticles can be induced to aggregate quickly in the presence of Hg(2+), especially with the assistance of ultraviolet radiation. The presence of Hg(2+) can be monitored by the colorimetric response of gold nanoparticles. The detection of Hg(2+) could be realized, after measuring the UV-vis spectra, with a detection limit of 100 nM. The selectivity of this method has been investigated by other divalent metal ions. The effective colorimetric sensor can be used for on-site and real-time Hg(2+) detection.

Gaseous mercury emissions from unsterilized and sterilized soils: the effect of temperature and UV radiation.

Mercury (Hg) emissions from the soils taken from two different sites (deciduous and coniferous forests) in the Adirondacks were measured in outdoor and laboratory experiments. Some of the soil samples were irradiated to eliminate biological activity. The result from the outdoor measurements with different soils suggests the Hg emission from the soils is partly limited by fallen leaves covering the soils which helps maintain relatively high soil moisture and limits the amount of heat and solar radiation reaching the soil surface. In laboratory experiments exposure to UV-A (365 nm) had no significant effect on the Hg emissions while the Hg emissions increased dramatically during exposure to UV-B (302 nm) light suggesting UV-B directly reduced soil-associated Hg. Overall these results indicate that for these soils biotic processes have a relatively constant and smaller influence on the Hg emission from the soil than the more variable abiotic processes.

Dissolved gaseous mercury production in the dark: Evidence for the fundamental role of bacteria in different types of Mediterranean water bodies.

It is well established that the dissolved gaseous mercury (DGM) production in waters is mainly driven by photochemical processes. The present paper provides evidence for a significant bacteria-mediated DGM production, occurring also under dark conditions in environmentally different types of coastal water bodies of the Mediterranean basin. The DGM production was laboratory determined in sea, lagoon-brackish and lake water samples, comparing the efficiency of the DGM production processes in darkness and in the light. This latter condition was established by exposing samples at solar radiation intensity in the Photosyntetical Active Radiation region (PAR) of 200 W m(-2). Mercury reduction rate in the dark was of the order of 2-4% of the DGM production in lightness, depending on the total mercury concentration in the water, rather than the bacterial abundance in it. Support for the active bacterial role in mercury reduction rate under dark conditions was provided by: 1) absence of significant DGM production in sterilized water samples (following filtration treatment or autoclaving), 2) restored DGM production efficiency, following re-inoculation into the same water samples of representatives of their bacterial community, previously isolated and separately cultured. Notwithstanding the low bacteria-mediated vs. the high photo-induced DGM production, whatever natural water body was considered, it is worth stressing the significant contribution of this organismal-mediated process to oceanic mercury evasion, since it occurs continuously along the entire water column throughout the 24 h of the day.

Photo-induced transformations of mercury(II) species in the presence of algae, Chlorella vulgaris.

The effects of algae (i.e., Chlorella vulgaris), Fe(III), humic substances, and pH on the photoreduction of Hg(II) under the irradiation of metal halide lamps (lambda>or=365 nm, 250 W) were investigated in this paper. The photoreduction rate of Hg(II) was found to increase with the increasing concentration of algae, Fe(III), and humic substances. The cooperation action of Fe(III) and humic substances accelerated the photoreduction of Hg(II). When the initial concentration of Hg(II) was in the range of 0.0-200.0 microg L(-1) with initial algae concentrations 7.0 x 10(9)cells L(-1) at pH 7.0, the initial photoreduction rate of Hg(II) could be expressed by the equation: -dC(Hg(II))/dt=0.65 x [C(Hg(II))](0.39) with a correlation coefficient of R=0.9912. The study on the photochemical process in terms of total mercury mass balance revealed that more than 40.86% of Hg(II) from the algal suspension was reduced to volatile metallic mercury. This paper discussed the photoreduction mechanism of Hg(II) in the presence of algae. This research will provide information for predicting the photoreduction of Hg(II) in the real environment. It will be helpful for understanding the photochemical transformation of Hg(II) and the formation of DGM in natural water in the presence of algae complexes. It will also be helpful for providing new methods to deal with heavy metal pollution.

Ultraviolet absorbance titration for determining stability constants of humic substances with Cu(II) and Hg(II).

We describe an ultraviolet (UV) absorbance titration method that can be used to determine complexing capacities (C(L)) and conditional stability constants (logK) of humic substances (HSs) with metal ions such as Cu(II) and Hg(II). Two fulvic acids (FA) and one humic acid (HA) were used for this study. UV absorbance of HSs gradually increased with the addition of Cu(II) or Hg(II) after blank correction, and these increases followed the theoretical 1:1 (ligand:metal ion) binding model. The results from the absorbance titration calculation for HSs with Cu(II) and Hg(II) compared well with those from fluorescence quenching titration. The titration of the model compound l-tyrosine with Cu(II) proved the validity of this method, and the K and C(L) were within 2.3% and 7.4% of the fluorescence quenching titration. The results suggest that the UV absorbance titration can be used to study the binding capacities of HSs and/or dissolved organic matter (DOM) with trace metals. The advantages and disadvantages of the absorbance titration method were also discussed.

Apparent rates of production and loss of dissolved gaseous mercury (DGM) in a southern reservoir lake (Tennessee, USA).

Apparent rates of dissolved gaseous mercury (DGM) concentration changes in a southern reservoir lake (Cane Creek Lake, Cookeville, Tennessee) were investigated using the DGM data collected in a 12-month study from June 2003 to May 2004. The monthly mean apparent DGM production rates rose from January (3.2 pg L(-1)/h), peaked in the summer months (June-August: 8.9, 8.0, 8.6 pg L(-1)/h), and fell to the lowest in December (1.6 pg L(-1)/h); this trend followed the monthly insolation march for both global solar radiation and UVA radiation. The monthly apparent DGM loss rates failed to show the similar trend with no consistent pattern recognizable. The spring and summer had higher seasonal mean apparent DGM production rates than the fall and winter (6.8, 9.0, 3.9, 5.0 pg L(-1)/h, respectively), and the seasonal trend also appeared to closely follow the solar radiation variation. The seasonal apparent DGM loss featured similar rate values for the four seasons (5.5, 4.3, 3.3, and 3.9 pg L(-1)/h for spring, summer, fall, and winter, respectively). Correlation was found of the seasonal mean apparent DGM production rate with the seasonal mean morning solar radiation (r=0.9084, p<0.01) and with the seasonal mean morning UVA radiation (r=0.9582, p<0.01). No significant correlation was found between the seasonal apparent DGM loss rate and the corresponding afternoon solar radiation (r=0.5686 for global radiation and 0.6098 for UVA radiation). These results suggest that DGM production in the lake engaged certain photochemical processes, either primary or secondary, but the DGM loss was probably driven by some dark processes.

Ratio of tritiated water and hydrogen generated in mercury through a nuclear reaction.

Tritium generated in a mercury target is a source of potential exposure of personnel at high-energy accelerator facilities. Knowledge of the chemical form of tritium is necessary to estimate the internal doses. We studied the tritium generation upon thermal neutron irradiation of a mercury target modified into liquid lithium amalgam to examine the ratio of tritiated water ([3H]H2O) and tritiated hydrogen ([3H]H2). The ratio between [3H]H2O and [3H]H2 generated in lithium amalgam was 4:6 under these experimental conditions.

Mercury emission to the atmosphere from experimental manipulation of DOC and UVR in mesoscale field chambers in a freshwater lake.

Mesocosm experiments in an optically transparent lake allow the manipulation of both dissolved organic carbon (DOC) and incident ultraviolet radiation (UVR) in order to study mercury reduction and emission processes. In the absence of UVR and the presence of visible light, mercury emission is very low (approximately0.3 ng/m2/h). When UVR is permitted in the mesocosm chambers, mercury emission increases, with emission rates ranging from 0.3 to 2.5 ng/m2/h. At concentrations between 1.5 and 2.5 mg/L DOC, mercury emission does not appear to depend on either the concentration or the optical properties of the DOC. In particular, the addition of 1.0 mg/L DOC from a nearby wetland to a photobleached mesocosm did not increase the emission of mercury. The similarities between mercury emission from highly photobleached 1.5 mg/L DOC and from terrestrially enriched 2.5 mg/L DOC suggest that the moieties responsible for mercury reduction are far in excess of that needed for mercury reduction. Using the measured flux rate of mercury from the water surface, we calculated a dissolved gaseous mercury (DGM) concentration thatwould need to be present to drive the emissive flux. The buildup of DGM was used to approximate a kinetic rate constant for the net mercury reduction in this system of approximately 0.17 h(-1), which is consistent with existing published values.

Atomistic simulations of electrowetting in carbon nanotubes.

Electrowetting of carbon nanotubes by mercury was studied using classical molecular dynamics simulations in conjunction with a macroscopic electrocapillarity model. A scaled ab initio mercury dimer potential, optimized to reproduce the mercury liquid density (at 300 K), melting point, and wetting angle on graphite, was selected for the simulations. Wetting of (20,20) single-walled carbon nanotubes by mercury occurs above a threshold voltage of 2.5 V applied across the interface. Both the electrocapillary pressure and imbibition velocity increase quadratically with voltage and can acquire large values, for example, 2.4 kbar and 28 m/s at 4 V, indicating a notable driving force. The observed voltage scaling can be captured by the Lucas-Washburn equation modified to include a wetting-line friction term.

Evaluation of focused ultrasound and ozonolysis as sample treatment for direct determination of mercury by FI-CV-AAS. Optimization of parameters by full factorial design.

Different oxidation methodologies based on ozone and focused ultrasound for the degradation of organic matter and organic-mercury compounds (spiked) present in human urine are discussed. Inorganic and total mercury can be determined in human urine. A flow-injection cold-vapour atomic absorption spectrometer system was used for mercury measurements. Optimization of cold vapour generation was performed with NaBH4 and SnCl2. A two-level full factorial design (2(4)) was applied to understand the cross-effects among the variables influencing the degradation of organic-mercurials and organic matter in urine by KMnO4/HCl/focused ultrasound, namely, KMnO4 and HCl concentration, ultrasonication time and ultrasonication amplitude. Optimization results showed that all variables were significant. New trends in the application of focused ultrasound and ozone are highlighted. As a result of the optimization procedure, one simple, rapid and accurate method was developed for the determination of total mercury in urine samples The method is based on the ultrasound assisted degradation of organo-mercurials and organic matter in urine in the presence of KMnO4/HCl/Focused Ultrasound. The procedure can be accomplished within 3 min, using 50% sonication amplitude provided by a probe ultrasonic device (63 W maximum output power, 22.5 kHz frequency). The method was applied to measure the mercury content in spiked urine from different non-exposed volunteers.

The influence of forestry activity on the structure of dissolved organic matter in lakes: implications for mercury photoreactions.

It is well known that dissolved organic matter (DOM) increases in lakes associated with forestry activity but characterization of the DOM structure is incomplete. Twenty-three lakes with a wide range of forestry activities located in central Quebec, Canada were sampled and analyzed for dissolved organic carbon (DOC) concentration, DOC fluorescence, and ultra violet-visible (UV-VIS) absorption spectra. The results show that DOC increases (as does the associated DOC fluorescence) with increased logging (slope=0.122, r2=0.581, p<0.001; and slope=0.283, r2=0.308, p<0.01, respectively) in the 23 lakes sampled however, the aromaticity of the DOM does not change with changes in logging (as found by UV-VIS ratios, absorbance slope in the UV region, and DOC normalized fluorescence (slope=1.42x10(-2), r2=0.331, p<0.01). The DOM from four of these lakes was concentrated using reverse osmosis (RO) followed by freeze-drying. The structures of the concentrated dissolved organic matter (DOM) samples were analyzed using X-ray analysis of near edge structures (XANES), X-ray diffraction (XRD), and 13C solid-state nuclear magnetic resonance (13C NMR) analysis. XANES analysis of functional groups in the four concentrated samples shows that there are significant differences in reduced sulphur between the samples, however there was no clear relationship with forestry activity in the associated catchment. XRD data showed the presence of amorphous sulphide minerals associated with the DOM concentrate that may be important sites for mercury binding. The 13C NMR spectra of these samples show that the percentage of carbon present in carboxylic functional groups increases with increasing logging. Such structures are important for binding photo-reducible mercury and their presence may limit mercury photo-reduction and volatilization. We propose a mechanism by which increased logging leads to increased carboxylic groups in DOM and thereby increased weak binding of photo-reducible mercury. These results, in part, explain the decrease in dissolved gaseous mercury (DGM) production rates with increased logging found in our previous work.

Radiation-induced site-specific damage of mercury derivatives: phasing and implications.

The behavior of mercury-derivatized triclinic crystals of a 60 kDa protein target from the New York Structural GenomiX Research Consortium provides novel insights into the mechanism of heavy-atom-specific radiation damage and its potential exploitation for de novo structure solution. Despite significant anomalous signal, structure solution by classic SAD and MAD phasing approaches was not successful. A detailed analysis revealed that significant isomorphic variation of the diffracted intensities was induced by X-ray irradiation. These intensity changes allowed the crystal structure to be solved by the radiation-damage-induced phasing (RIP) technique. Inspection of the crystal structure and electron-density maps demonstrated that the covalent S-Hg bonds at all four derivatized cysteine sites were much more susceptible to radiation-induced cleavage than other bonds typically present in native proteins. A simple diagnostic is described to identify the fingerprint of such decay at the time of data collection/processing. The rapid radiation-induced decomposition of mercury adducts is consistent with the difficulties frequently associated with the experimental phasing of mercury derivatives and suggests a straightforward solution to overcome this limitation by radiation-damage-induced phasing with anomalous scattering (RIPAS). These results indicate that historically recalcitrant and newly emerging difficulties associated with Hg phasing should be revisited.

Rapid release of mercury from intertidal sediments exposed to solar radiation: a field experiment.

There is increasing evidence of the primary importance of photochemical reactions and transfer of gaseous mercury to the atmosphere. Although mercury in aquatic sediments is efficiently retained, resuspension and bioturbation in intertidal sediments may expose temporarily anoxic sediments to solar radiation. Field experiments were performed to investigate these processes. Anoxic sediments from two areas in the Tagus estuary with different degrees of Hg contamination (experiments I and II) were homogenized and distributed into two sets of 36 uncovered Petri dishes. The samples were placed on the intertidal sediments and exposed to direct solar radiation and kept under dark (control) for 6-8 h. The decrease rates of acid volatile sulfides (abrupt in the first 3 h) and of pyrite (linear) were the same in sediments under solar radiation and dark. The total Hg concentrations were relatively constant in sediments kept in dark, but decreased from 17.6 to 7.65 and 3.45 to 1.35 nmol g(-1) in experiments I and II, respectively. In those exposed to solar radiation during the period of higher UV intensity. Similar evolutions were found in nonreactive Hg in pore waters (3.00-2.59 and 0.725-0.105 nM). On the contrary, reactive Hg was higher in pore waters of the sediments exposed to solar radiation and increased with time, from 424 to 845 pM and 53 to 193 pM. These results indicate that most mercury released in pore waters was photochemically reduced in a short period of time and escaped rapidly to the atmosphere. Episodes of bottom resuspension and bioturbation in the intertidal sediments enhance the transfer of gaseous mercury to the atmosphere.