Environmental and human exposure assessment monitoring of communities near an abandoned mercury mine in the Philippines: a toxic legacy

Abandoned mines are an important global concern and continue to pose real or potential threats to human safety and health including environmental damage/s. Very few countries had government mine regulation and reclamation policies until the latter part of the century where legal, financial and technical procedures were required for existing mining operations. Major reasons for mine closure may be mainly due to poor economies of the commodity making mining unprofitable, technical difficulties and national security. If the mine is abandoned, more often than not it is the government that shoulders the burden of clean-up, monitoring and remediation. The topic of abandoned mines is complex because of the associated financial and legal liability implications. Abandoned mercury mines have been identified as one of the major concerns because of their significant long-term environmental problems. Primary mercury production is still ongoing in Spain, Kyrgzystan, China, Algeria, Russia and Slovakia while world production declined substantially in the late 1980s. In the Philippines, the mercury mine located southeast of Manila was in operation from 1955 to 1976, before ceasing operation because of the decline in world market price for the commodity. During this time, annual production of mercury was estimated to be about 140,000 kg of mercury yearly. Approximately 2,000,000 t of mine-waste calcines (retorted ore) were produced during mining and roughly 1,000,000 t of these calcines were dumped into nearby Honda Bay to construct a jetty to facilitate mine operations where about 2000 people reside in the nearby three barangays. In October, 1994 the Department of Health received a request from the Provincial Health Office for technical assistance relative to the investigation of increasing complaints of unusual symptoms (e.g. miscarriages, tooth loss, muscle weakness, paralysis, anemia, tremors, etc.) among residents of three barangays. Initial health reports revealed significant elevation of blood mercury levels exceeding the then recommended exposure level of 20ppb in 12 out of the 43 (27.9%) residents examined. The majority of the volunteers were former mine workers. In this study the abnormal findings included gingivitis, mercury lines, gum bleeding and pterydium. The most common neurologic complaints were numbness, weakness, tremors and incoordination. Anemia and elevated liver function tests were also seen in a majority of those examined. The assessment also revealed a probable association between blood mercury level and eosinophilia. The same association was also seen between high mercury levels and the presence of tremors and working in the mercury mine. To date, there are very limited environmental and health studies on the impact of both total and methylmercury that have been undertaken in the Philippines. Thus, this area of study was selected primarily because of its importance as an emerging issue in the country, especially regarding the combined effects of total and methylmercury low-dose and continuous uptake from environmental sources. At present the effects of total mercury exposure combined with MeHg consumption remain an important issue, especially those of low-dose and continuous uptake. Results of the study showed that four (4) species of fish, namely ibis, tabas, lapu-lapu and torsillo, had exceeded the recommended total mercury and methylmercury levels in fish (NV>0.5 microg/gf.w., NV>0.3 microg/gf.w., respectively). Saging and kanuping also exceeded the permissible levels for methylmercury. Total and methylmercury in canned fish, and total mercury in rice, ambient air and drinking water were within the recommended levels, however, additional mercury load from these sources may contribute to the over-all body burden of mercury among residents in the area. Surface water quality at the mining area, Honda Bay and during some monitoring periods at Palawan Bay exceeded total mercury standards (NV>0.002 ng/mL). Soil samples in two sites, namely Tagburos and Honda Bay, exceeded the EPA Region 9 Primary Remediation Goal recommended values for total mercury for residential purposes (NV>23 mg/kg). The hand to mouth activity among infants and children is another significant route for mercury exposure. Statistically significant results were obtained for infants when comparing the results after one year of monitoring for methylmercury levels in hair for both exposed and control sub-groups. Likewise, comparing the initial and final hair methylmercury levels among pregnant women/mothers in the exposed group showed statistically significant (p<0.05) results. Comparing the exposed and control sub-groups' mercury hair levels per sub-group showed statistically significant results among the following: (a) initial and final total mercury hair levels among children, (b) initial and final methylmercury hair levels among children, (c) final total mercury hair levels among pregnant women, (d) initial and final total mercury hair levels among mothers, and (e) initial and final methyl hair levels among mothers.     

Pathways and products of the degradation of PCBs by the sodium dispersion method

Nine polychlorinated biphenyl (PCB) congeners (2-chlorobiphenyl, 3-chlorobiphenyl, 4-chlorobiphenyl, 2,3,4-trichlorobiphenyl, 2,2',5,5'-tetrachlorobiphenyl, 2,3',4,4',5-pentachlorobiphenyl, 3,3',4,4',5-pentachlorobiphenyl, 2,2',4,4',5,5'-hexachlorobiphenyl, and decachlorobiphenyl) were dechlorinated by the sodium dispersion method (SD) at low temperature (60 degrees C). The dechlorination of 4-chlorobiphenyl was the fastest among the three monochlorobiphenyls. As for the other six congeners, we investigated the major dechlorination pathways. Although reaction selectivity was not very sensitive to the position of the chlorine substituent, the chlorines at the para position were slightly easier to dechlorinate than those at the ortho or meta positions. The decomposition rate increased with the total numbers of chlorine substituents. A chlorine situated between two other chlorines showed a high reactivity. When the numbers of chlorines on each of the phenyl rings were different, the reactions occurred on the more substituted ring. In the degradation of 4-chlorobiphenyl at elevated temperature (160 degrees C), we investigated the structures of the polymerized products and whether all the organic chlorinated compounds degraded finally or not. As for the dimers, p-quarterphenyl (QP) and m,p-QP were detected but not o-QP, m-QP, o,p-QP, o,m-QP, or the mono- to tetra-chlorinated QPs. Compounds with a molecular weight of 534.4183 or 758.6713 were detected. They were considered to have C40H54 or C56H86 as their molecular formula. The compounds were most probably the polymerized products resulting from coupling of hexadecane or two hexadecanes and two phenylcyclohexadienes. It was thought the dechlorination and the polymerization were the main reactions. All of many detected compounds were hydrocarbons without chlorines, and no peaks originating from organic chlorinated compounds were observed by mass spectroscopic (MS) methods.     

Dynamics of gonadosomatic index of fish with indeterminate fecundity between subsequent egg batches: application to Japanese anchovy Engraulis japonicus under captive conditions

The gonadosomatic index (GSI) is widely used as a simple measure of reproductive capacity, but its validity has often been questioned. This study showed the inter-spawning variation in the predicted GSI of Japanese anchovy using the gravimetric oocyte packing density method. Time course sampling showed that final oocyte maturation and subsequent ovulation occurred from afternoon to evening on the day of spawning. Oocyte in vitro assay, however, suggested that the timing of the spawning could be predetermined by midnight the day before spawning. Models predicted that the GSI of a female just after spawning gradually increases until the completion of germinal vesicle breakdown, after which it dramatically rises by 24–53 % per hour within a few hours of the onset of ovulation. This indicates that the predicted GSI of a female increases by 3.5 times within about 19 h before ovulation, even if the relative batch fecundity remains constant.     

Maturity classification and group maturity of the red sea bream Pagrus major

The criteria of ovarian maturity during the spawning season and maturity rates according to age are described for the female red sea bream Pagrus major collected from the Chikuzenkai between April and June, 1984. The degree of maturity of the ovary is categorized into four stages based on the maturation stage of the most advanced oocytes in the ovary, rate of atresia and occurrence of post-ovulatory follicles. The ovarian maturity rates in fish aged 2, 3, 4 and 5 years were shown to be 5.8, 46.2, 75.0 and 97.3%, respectively, assuming that yolked ovaries with low levels of atresia (<50% yolked oocytes affected) attain maturity. The fork length at which 50% of the fish attained maturity ranged from 280 to 300 mm.     

Production and characterization of KOH-activated carbon derived from polychlorinated biphenyl residue generated by the sodium dispersion process

Polychlorinated biphenyl (PCB) residues from the sodium dispersion (SD) process were employed as the raw materials for the production of activated carbon using KOH activation. The pore properties, such as the specific surface area and pore size distribution, were characterized using the Barrett–Joyner–Halenda method and the Horvath–Kawazoe method based on the N₂ adsorption isotherm at 77 K. The activated carbon produced showed similar adsorption capacities and specific surface areas to the commercially available product. The effects of the activation conditions on the porosity of the activated carbon produced were studied. The most significant factor affecting the specific surface proved to be the activation temperature. The activated carbon produced from PCB residues from the high-temperature (423–443 K) SD process had a binary pore size distribution well developed in the 4 nm region and in the micropore region. The pore structure of the carbon produced from PCB residues from the low-temperature (333–393 K) SD process had a wide range of micropores and mesopores.     

Lack of genotoxic potential of permethrin in mice evaluated by the comet assay and micronucleus test

Permethrin is a common insecticide that does not show genotoxic potential in standard in vitro and in vivo assays. To investigate the genotoxic potential of permethrin in more detail, two in vivo studies were conducted on female mice to assess DNA damage in tumor target organs by the comet assay and micronucleus test. For this, mice were administered permethrin at doses of 150, 300, or 600 mg/kg/day by gavage for 2 days, and their lung, liver, glandular stomach, peripheral blood, and bone marrow cells were examined for DNA damage. There were no significant increases in % tail DNA in the organs examined and no increase in micronuclei in peripheral blood by flow cytometry. Taken together, the present findings provide evidence that permethrin has no genotoxic, aneugenic, or clastogenic potential.     

Recombinant human AhR-mediated GUS reporter gene assays for PCB congeners in transgenic tobacco plants in comparison with recombinant mouse and guinea pig AhRs

Four expression plasmids for recombinant human aryl hydrocarbon receptor (hAhR) consisting of a ligand binding domain of hAhR, a DNA-binding domain of LexA and a transactivation domain of VP16 as well as β-glucuronidase (GUS) reporter genes were constructed. All the expression plasmids were transformed into tobacco plants. The selected transgenic tobacco plants were used to assay. PCB congeners showed GUS activity in a TEF-dependent manner. The selected transgenic tobacco plant XhD4V17 was compared with the transgenic tobacco plants XmD4V26 and XgD2V23 containing recombinant mouse (m) AhR-mediated GUS reporter gene expression cassette and recombinant guinea pig (g) AhR-mediated GUS reporter gene expression cassette for PCB congener-inducible GUS activity. The data revealed that the tobacco plant XgD2V23 was the most active in PCB congener-inducible GUS activity. In a 1:1 mixture of PCB126 and PCB80 a reduced PCB126-induced GUS activity was observed in plant XgD2V23, which could possibly be due to interaction between PCB126 and PCB80.     

Online measurements of low-volatile organic chlorine for dioxin monitoring at municipal waste incinerators

In this study, an automatic sampling device and an analysis device have been developed for the measurement of low-volatile organic chlorine (LVOCl) in flue gas. The concentrations of dioxins (polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and dioxin-like polychlorinated biphenyls) have been estimated by online measurements of LVOCl at a municipal solid waste incinerator (MSWI) using these devices. The LVOCl concentration at the outlet of the selective catalyst reactor (SCR) of the MSWI increased momentarily up to 95 μg Cl m⁻³ during the startup period of the MSWI; subsequently, it gradually decreased to less than 1.0 μg Cl m⁻³ after 50 h from the start of waste feeding. The concentration of toxic equivalent quantity (TEQ)-Dioxins at the SCR outlet had a linear positive relationship with the LVOCl concentrations. Moreover, the level of TEQ-Dioxins concentration can be estimated by using this relationship with LVOCl. From our results, since the LVOCl concentrations in a flue gas can thus be automatically analyzed every hour by online measurements, the operators of an MSWI would be able to monitor approximate TEQ-Dioxin emissions on a daily basis.     

Development of active and diffusive sampling methods for determination of 3-methoxybutyl acetate in workplace air

Monitoring of the workplace concentration of 3-methoxybutyl acetate (MBA), which is used in printer's ink and thinner for screen-printing and as an organic solvent to dissolve various resins, is important for health reasons. An active and a diffusive sampling method, using a gas chromatograph equipped with a flame ionization detector, were developed for the determination of MBA in workplace air. For the active sampling method using an activated charcoal tube, the overall desorption efficiency was 101%, the overall recovery was 104%, and the recovery after 8 days of storage in a refrigerator was more than 90%. For the diffusive sampling method using the 3M 3500 organic vapor monitor, the MBA sampling rate was 19.89 cm(3) min(-1). The linear range was from 0.01 to 96.00 microg ml(-1), with a correlation coefficient of 0.999, and the detection limits of the active and diffusive samplers were 0.04 and 0.07 microg sample(-1), respectively. The geometric mean of stationary sampling and personal sampling in a screen-printing factory were 12.61 and 16.52 ppm, respectively, indicating that both methods can be used to measure MBA in workplace air.