Evaluation of mercury in a freshwater environment impacted by an organomercury fungicide using diffusive gradient in thin films.

The use of pesticides to manage pest problems for crop protection is common practice around the world, and their accumulation in soils and contamination of water bodies is a global environmental problem. In Australia, an organomercury (Hg)-based fungicide is the most popular for control of pineapple disease of sugarcane. However, the presence of Hg is of great concern because of potential adverse effects in the environment. The purpose of this work was to evaluate the residual levels of Hg in soils of sugarcane cultivation from a catchment in North Queensland (Australia). Mercury was surveyed in soils close to the Tully River at 3 different depths (100, 200 and 300mm). Additionally, total Hg (THg) and the labile fraction of Hg in water (measured by the diffusive gradient in thin film technique) were determined in the Tully River. A pristine site, the Tully Gorge National Park upstream of sugarcane fields, was selected for background Hg concentration estimation. In soils, Hg levels ranged from 18 to 264µgkg-1, with one of the soil samples being almost 10 times higher than at other sites at the surface level (199µgkg-1). Total and labile concentrations of Hg in water increased from the Hg-elevated soil sampling sites (0.085µgL-1 and 0.061µgL-1) to downstream sites (0.082µgL-1 and 0.066µgL-1), which is likely due to agricultural runoff. Indeed, except for the upstream control site, the THg concentration in water is over the limit permitted by the Australian freshwater quality guideline for protection of 99% species (0.06µgL-1). These findings point to the need to perform further research to reveal the mechanisms for release of Hg from soil and whether this might be causing important adverse effects to the Great Barrier Reef located in front of this river catchment.

Metal Concentrations and Responses of Chironomid Larvae Exposed to Thailand Pulp and Paper Mill Effluent.

Pulp and paper mills (PPM) may discharge insufficiently treated waste into rivers and give rise to serious effects with aquatic life. This study investigated the biological response of the chironomid (Chironomus javanus, Kieffer) when exposed to PPM effluent. Effluent concentrations of BOD, COD, TKN, TS, Cr, Cu, Pb and Zn were high. Cd and Cr concentrations in chironomid were the most accumulated. Whole effluent toxicity on the chironomid test organism was significant as expressed by the percent survival and decreased with increasing concentration. Highest dry weight, head capsule and length of the chironomid test organism corresponded to 100% effluent at a specific time. Effect of dilution was assessed by using glutathione S-transferase activity on chironomid and corresponded to 6.25% effluent during 48-96 h which was significantly increased in the chironomid. The results showed that the chironomid was sensitive to PPM effluent and toxicity tests can be used for assessing the effect of effluent on aquatic species.

Sources, distribution, bioavailability, toxicity, and risk assessment of heavy metal(loid)s in complementary medicines.

The last few decades have seen the rise of alternative medical approaches including the use of herbal supplements, natural products, and traditional medicines, which are collectively known as 'Complementary medicines'. However, there are increasing concerns on the safety and health benefits of these medicines. One of the main hazards with the use of complementary medicines is the presence of heavy metal(loid)s such as arsenic (As), cadmium (Cd), lead (Pb), and mercury (Hg). This review deals with the characteristics of complementary medicines in terms of heavy metal(loid)s sources, distribution, bioavailability, toxicity, and human risk assessment. The heavy metal(loid)s in these medicines are derived from uptake by medicinal plants, cross-contamination during processing, and therapeutic input of metal(loid)s. This paper discusses the distribution of heavy metal(loid)s in these medicines, in terms of their nature, concentration, and speciation. The importance of determining bioavailability towards human health risk assessment was emphasized by the need to estimate daily intake of heavy metal(loid)s in complementary medicines. The review ends with selected case studies of heavy metal(loid) toxicity from complementary medicines with specific reference to As, Cd, Pb, and Hg. The future research opportunities mentioned in the conclusion of review will help researchers to explore new avenues, methodologies, and approaches to the issue of heavy metal(loid)s in complementary medicines, thereby generating new regulations and proposing fresh approach towards safe use of these medicines.

Nickel biopathways in tropical nickel hyperaccumulating trees from Sabah (Malaysia).

The extraordinary level of accumulation of nickel (Ni) in hyperaccumulator plants is a consequence of specific metal sequestering and transport mechanisms, and knowledge of these processes is critical for advancing an understanding of transition element metabolic regulation in these plants. The Ni biopathways were elucidated in three plant species, Phyllanthus balgooyi, Phyllanthus securinegioides (Phyllanthaceae) and Rinorea bengalensis (Violaceae), that occur in Sabah (Malaysia) on the Island of Borneo. This study showed that Ni is mainly concentrated in the phloem in roots and stems (up to 16.9% Ni in phloem sap in Phyllanthus balgooyi) in all three species. However, the species differ in their leaves - in P. balgooyi the highest Ni concentration is in the phloem, but in P. securinegioides and R. bengalensis in the epidermis and in the spongy mesophyll (R. bengalensis). The chemical speciation of Ni2+ does not substantially differ between the species nor between the plant tissues and transport fluids, and is unambiguously associated with citrate. This study combines ion microbeam (PIXE and RBS) and metabolomics techniques (GC-MS, LC-MS) with synchrotron methods (XAS) to overcome the drawbacks of the individual techniques to quantitatively determine Ni distribution and Ni2+ chemical speciation in hyperaccumulator plants.

Bioavailability study of arsenic and mercury in traditional Chinese medicines (TCM) using an animal model after a single dose exposure.

Traditional Chinese medicines (TCM) are increasingly being used as alternative medicines in many countries, and this has caused concern because of adverse health effects from toxic metal bioavailability such as mercury (Hg) and arsenic (As). The aim of this study was to investigate the bioavailability of As and Hg from TCM after a single exposure dose using an animal model of female Sprague-Dawley rats. The rats were divided into 6 groups which included four groups treated with sodium arsenite (NaAsO2), arsenic sulfide (As2S3), mercuric chloride (HgCl2), mercuric sulfide (HgS), and two groups treated with TCM containing high Hg or As (Liu Shen Wan: As 7.7-9.1% and Hg 1.4-5.0%; Niuhang Jie du Pian: As 6.2-7.9% and Hg <0.001%). The samples of urine, faeces, kidney and liver were collected for analysis and histological assay. The results indicated that relatively low levels of As and Hg from these TCM were retained in liver and kidney tissues. The levels of As in these tissues after TCM treatment were consistent with the levels from the As sulphide treated group. With the exception of the mercuric chloride treated group, the levels of Hg in urine from other groups were very low, and high levels of As and Hg from TCM were excreted in faeces. The study showed poor bioavailability of As and Hg from TCM as indicated by low relative bioavailability of As (0.60-1.10%) and Hg (<0.001%). Histopathological examination of rat kidney and liver tissues did not show toxic effects from TCM.

In situ analysis of foliar zinc absorption and short-distance movement in fresh and hydrated leaves of tomato and citrus using synchrotron-based X-ray fluorescence microscopy.

BACKGROUND AND AIMS: Globally, zinc deficiency is one of the most important nutritional factors limiting crop yield and quality. Despite widespread use of foliar-applied zinc fertilizers, much remains unknown regarding the movement of zinc from the foliar surface into the vascular structure for translocation into other tissues and the key factors affecting this diffusion. METHODS: Using synchrotron-based X-ray fluorescence microscopy (µ-XRF), absorption of foliar-applied zinc nitrate or zinc hydroxide nitrate was examined in fresh leaves of tomato (Solanum lycopersicum) and citrus (Citrus reticulatus). KEY RESULTS: The foliar absorption of zinc increased concentrations in the underlying tissues by up to 600-fold in tomato but only up to 5-fold in citrus. The magnitude of this absorption was influenced by the form of zinc applied, the zinc status of the treated leaf and the leaf surface to which it was applied (abaxial or adaxial). Once the zinc had moved through the leaf surface it appeared to bind strongly, with limited further redistribution. Regardless of this, in these underlying tissues zinc moved into the lower-order veins, with concentrations 2- to 10-fold higher than in the adjacent tissues. However, even once in higher-order veins, the movement of zinc was still comparatively limited, with concentrations decreasing to levels similar to the background within 1-10 mm. CONCLUSIONS: The results advance our understanding of the factors that influence the efficacy of foliar zinc fertilizers and demonstrate the merits of an innovative methodology for studying foliar zinc translocation mechanisms.

Bioavailability and pharmacokinetics of arsenic are influenced by the presence of cadmium.

Mine wastes contain a mixture of metals and metalloids including arsenic (As) and cadmium (Cd). This study investigated the potential interaction between As and Cd in a rat model. Sprague Dawley rats were dosed with sodium arsenate via the oral (0, 0.5, 5 and 15 mg As kg(-1) b.w.) or intravenous (0.5 mg As kg(-1) b.w.) route to establish its dose-response relationship in terms of bioavailability and pharmacokinetic parameters. Bioavailability of As reduced when the dose of As increased. For the interaction study a fixed oral dose of As at 2.5 mg As kg(-1) b.w. solo and in combination with Cd as cadmium chloride at 3 or 6 mg Cd kg(-1) b.w. were administered to rats. Bioavailability of As was decreased by 34-35% in the presence of Cd. Elimination half-life of As was also decreased from 69 days in the As solo group to 13-22 days in the presence of 3 and 6 mg Cd kg(-1) b.w. respectively. Decreased urinary excretion of As and tissue accumulation were also observed. A probable explanation for these findings is that As co-administration with Cd could have resulted in the formation of less soluble cadmium-arsenic complexes in the guts of the rats. Nevertheless, such an interaction between As and Cd could only explained about 44-48% of the variation when mine waste materials containing both of these elements were administered to rats. This suggests other physical properties and chemical compound formation could contribute to the observed bioavailability of arsenic in complex environmental samples.

Human health risk assessment of lead from mining activities at semi-arid locations in the context of total lead exposure.

Lead from historical mining and mineral processing activities may pose potential human health risks if materials with high concentrations of bioavailable lead minerals are released to the environment. Since the Joint Expert Committee on Food Additives of Food and Agriculture Organization/World Health Organization withdrew the Provisional Tolerable Weekly Intake of lead in 2011, an alternative method was required for lead exposure assessment. This study evaluated the potential lead hazard to young children (0-7 years) from a historical mining location at a semi-arid area using the U.S. EPA Integrated Exposure Uptake Biokinetic (IEUBK) Model, with selected site-specific input data. This study assessed lead exposure via the inhalation pathway for children living in a location affected by lead mining activities and with specific reference to semi-arid conditions and made comparison with the ingestion pathway by using the physiologically based extraction test for gastro-intestinal simulation. Sensitivity analysis for major IEUBK input parameters was conducted. Three groups of input parameters were classified according to the results of predicted blood concentrations. The modelled lead absorption attributed to the inhalation route was lower than 2 % (mean ± SE, 0.9 % ± 0.1 %) of all lead intake routes and was demonstrated as a less significant exposure pathway to children's blood, compared with ingestion. Whilst dermal exposure was negligible, diet and ingestion of soil and dust were the dominant parameters in terms of children's blood lead prediction. The exposure assessment identified the changing role of dietary intake when house lead loadings varied. Recommendations were also made to conduct comprehensive site-specific human health risk assessment in future studies of lead exposure under a semi-arid climate.

Interaction effects of lead on bioavailability and pharmacokinetics of arsenic in the rat.

Arsenic (As) and lead (Pb) are common contaminants found in mine waste materials. For an evidence-based risk assessment, it is important to better understand the potential interaction of mixed contaminants; and this interaction study was investigated in an in vivo rat model. Following co-administration of a fixed dose of As(V) as in sodium arsenate and different doses of Pb as lead acetate to Sprague-Dawley rats, blood arsenic concentration and bioavailability decreased. A decrease in As blood concentration when lead was co-administered was observed with increasing lead doses. Pharmacokinetic parameters for As in the blood showed faster absorption and elimination of this metalloid in the presence of Pb. The elimination half-life of As decreased from 67 days in As solo group to 27-30 with doses of Pb. Bioavailability of As was also decreased by 30-43 % in the presence of Pb. Decreased urinary excretion of Pb and tissue accumulation were also observed. It indicates lower absorption of As when co-administered with Pb. A probable explanation for these findings is that As co-administration with Pb could have resulted in the formation of less soluble lead arsenate. However, such an interaction between As and Pb could only explain about one-third of the variation when real mine waste materials containing both of these elements were administered to rats. This suggests that other effects from physical and chemical parameters could contribute to the bioavailability of arsenic in complex real environmental samples.

Evaluation and application of the diffusive gradients in thin films technique using a mixed-binding gel layer for measuring inorganic arsenic and metals in mining impacted water and soil.

The diffusive gradients in thin films (DGT) equipped with a Chelex or ferrihydrite binding gel has been designed to enable the measurement of either labile metal species or inorganic arsenic, respectively. In the mine impacted environment, metals and metalloids commonly coexist in a variety of species. This study, for the first time reports the performance of the DGT with a mixed-binding layer (MBL), consisting of Chelex and ferrihydrite for measurements of both metals and arsenic in a single assay. The MBL that consists of a combination of Chelex and ferrihydrite at a ratio of 1:2 has the greatest binding capacity for arsenic (As), cadmium (Cd), copper (Cu), lead (Pb), and zinc (Zn). The elemental concentrations measured by using MBL-DGT (C(DGT)) were comparable (92-104%) with the original test solution concentrations (C(SOL)). The measurement of As by using MBL-DGT was consistent across a wide pH range (3-8) and ionic strength (0.001-0.1 M). At high pH (9), As measurement was slightly affected (∼80%). The measurements of Cd, Pb, and Zn were affected at low pH (<3) and high pH (9). Measurements of Cd, Cu, and Pb were affected at low ionic strength (0.001 M). At high ionic strength (0.1 M), measurements of Cd; Cu and Pb were slightly affected. The capacity of MBL-DGT for quantitative measurement in a multielements solution is effectively limited to 15 µg for As and 70 µg for metals per MBL-DGT device. Good correlations (p < 0.01) between MBL-DGT measurements and ferrihydrite or Chelex DGT were obtained for As, Cd, Cu, Pb, and Zn in water and soil with exception for Cd and Cu (p < 0.05) when deployed in soil.

Dissolved organic carbon reduces uranium toxicity to the unicellular eukaryote Euglena gracilis.

The influence of dissolved organic carbon (DOC), in the form of Suwannee River fulvic acid (SRFA), on uranium (U) toxicity to the unicellular eukaryote, Euglena gracilis (Z strain), was investigated at pH 6. In a background medium without SRFA, exposure of E. gracilis to 57 µg L(-1) U resulted in a 50% reduction in growth (IC(50)). The addition of 20 mg L(-1) DOC (as SRFA), reduced U toxicity 4 to 5-fold (IC(50) increased to 254 µg L(-1) U). This reduction in toxicity was also evident at more sensitive effect levels with a 10% reduction in growth (IC(10)) occurring at 5 µg L(-1) U in the background medium and at 17 µg L(-1) U in the SRFA medium, respectively. This amelioration of toxicity with the addition of SRFA was linked to a decrease in the bioavailability of U, with geochemical speciation modelling predicting 84% of U would be complexed by SRFA. The decrease in bioavailability of U in the presence of SRFA was also evident from the 11-14 fold reduction in the cellular concentration of U compared to that of E. gracilis in the background medium. Stepwise multiple linear regression analyses indicated that UO(2)(2+) alone explained 51% of the variation in measured U toxicity to E. gracilis. Preliminary U exposures to E. gracilis in the presence of a reactive oxygen species probe, suggest exposure to ≥60 µg L(-1) U may induce oxidative stress, but this endpoint was not considered to be a sensitive biological indicator.

Dissolved organic carbon reduces the toxicity of aluminum to three tropical freshwater organisms.

The influence of dissolved organic carbon (DOC) on the toxicity of aluminum (Al) at pH 5 (relevant to acid mine drainage conditions), to the tropical green hydra (Hydra viridissima), green alga (Chlorella sp.), and cladoceran (Moinodaphnia macleayi) was assessed. Two DOC sources, a natural in situ DOC in soft billabong water (SBW) and Suwannee River fulvic acid (SRFA) standard, were compared. The order of sensitivity of the test organisms to dissolved Al (0.1 µm fraction) was Hydra viridissima > Moinodaphnia macleayi > Chlorella sp. with DOC reducing dissolved Al toxicity most for Hydra viridissima. However, colloidal or precipitated Al may contribute indirectly to the toxicity for M. macleayi and Chlorella sp. The toxicity of dissolved Al was up to six times lower in test waters containing 10 mg L(-1) DOC (in the form of SRFA), relative to toxicity observed at 1 mg L(-1) DOC. In contrast, the toxicity of Al was up to two times lower in SBW containing 10 mg L(-1) DOC, relative to water containing 1 mg L(-1) DOC. The increased ability of SRFA in reducing Al toxicity was linked to its greater affinity for complexing Al compared with the in situ DOC. This has important implications for studies that use commercial standards of humic substances to predict Al toxicity in local environments. Speciation modeling demonstrated that Al(3+) and AlOH(2+) provided a strong relationship with toxicity. An empirical relationship is provided for each organism that can be used to predict Al toxicity at a given Al and DOC concentration.

Dissolved organic carbon reduces uranium bioavailability and toxicity. 2. Uranium[VI] speciation and toxicity to three tropical freshwater organisms.

The influence of dissolved organic carbon (DOC) on the toxicity of uranium (U) to three Australian tropical freshwater species, the Northern Trout Gudgeon (Mogurnda mogurnda), green hydra (Hydra viridissima) and unicellular green alga (Chlorella sp.) was assessed. Exposures were conducted in synthetic soft water without DOC and with DOC added in the form of standard Suwannee River Fulvic Acid (SRFA). Organisms were exposed to a range of U concentrations at a range of DOC concentrations (0-20 mg L(-1)). U toxicity was up to 20 times less in water containing 20 mg L(-1) DOC, relative to DOC-free test waters. U toxicity was also assessed using natural water from a tropical Australian billabong containing 10 mg L(-1) DOC. U toxicity was up to ten times less in the billabong water, relative to DOC--free test waters. SRFA was twice as effective at reducing U toxicity as the billabong water at equivalent DOC concentrations. Geochemical speciation modeling confirmed the decreased U toxicity that resulted from both DOC sources was primarily due to a decrease in the free uranyl ion (UO2(2+)) through complexation with DOC. A predictive model is presented for each of the organisms that can be used to predict U toxicity at a given U and DOC concentration.

Dissolved organic carbon reduces uranium bioavailability and toxicity. 1. Characterization of an aquatic fulvic acid and its complexation with uranium[VI].

Fulvic acid (FA) from a tropical Australian billabong (lagoon) was isolated with XAD-8 resin and characterized using size exclusion chromatography, solid state cross-polarization magic angle spinning, 13C nuclear magnetic resonance spectroscopy, elemental analysis, and potentiometric acid-base titration. Physicochemical characteristics of the billabong FA were comparable with those of the Suwannee River Fulvic Acid (SRFA) standard. The greater negative charge density of the billabong FA suggested it contained protons that were more weakly bound than those of SRFA, with the potential for billabong water to complex less metal contaminants, such as uranium (U). This may subsequently influence the toxicity of metal contaminants to resident freshwater organisms. The complexation of U with dissolved organic carbon (DOC) (10 mg L(-1)) in billabong water was calculated using the HARPHRQ geochemical speciation model and also measured using flow field-flow fractionation combined with inductively coupled plasma mass-spectroscopy. Agreement between both methods was very good (within 4% as U-DOC). The results suggest that in billabong water at pH 6.0, containing an average DOC of 10 mg L(-1) and a U concentration of 90 µg L(-1), around 10% of U is complexed with DOC.

Consistent chemical form of Cd in liver and kidney tissues in rats dosed with a range of Cd treatments: XAS of intact tissues.

X-ray absorption spectroscopy of frozen intact tissues shows that in rats exposed to a range of treatments involving cadmium, alone or in combination with other metal ions, the coordination environment of cadmium is consistent in both the liver and kidney. Comparison of the spectra from the rat tissues to biologically relevant model compounds indicates that the vast majority of the cadmium is bound to metallothionein in these tissues.

Ecotoxicological assessment of diffuse pollution using biomonitoring tool for sustainable land use in Thailand.

As a developing country, Thailand has a significant issue with diffuse pollution of the soil ecosystem due to an indiscriminate use of agrichemicals and poorly regulated disposal of a wide variety of hazardous wastes. Practical risk assessment tools based on locally-occurring species are needed to assess the effects of diffuse pollutants on the soil ecosystem in Thailand because reliance on soil criteria developed for overseas conditions may provide inadequate protection. Native soil organisms in Thailand may be more or less sensitive to contaminants compared to overseas test species. This article described a biological indicator approach for ecological risk assessment of diffuse pollution in the soil ecosystem of Thailand from pesticide application with the aim of developing standardized protocols using native species and locally generated data to better evaluate the ecological risks of non-point source soil pollution. It was found that ecotoxicological assessment provided a better understanding of the ecological impacts that diffuse pollution induced on Thai environmental conditions. Thai soil biota species were more sensitive to soil contaminants than similar species overseas. Soil series also had an influence on the ecotoxicology of contaminants to soil biota. Collembolan, Cyphoderus sp., was demonstrated as a useful alternative test species to Folsomia candida (international test species) for terrestrial ecotoxicological testing of Thai soils. In addition, the soil biota activities such as soil respiration and earthworm avoidance including soil biodiversity and the litter bag decomposition technique are also good tools to assess the effects of diffuse pollution by pesticides on the soil ecosystem of Thailand.

Effects of residues from municipal solid waste landfill on corn yield and heavy metal content.

The effects of residues from municipal solid waste landfill, Khon Kaen Municipality, Thailand, on corn (Zea mays L.) yield and heavy metal content were studied. Field experiments with randomized complete block design with five treatments (0, 20, 40, 60 and 80% v/v of residues and soil) and four replications were carried out. Corn yield and heavy metal contents in corn grain were analyzed. Corn yield increased by 50, 72, 85 and 71% at 20, 40, 60 and 80% treatments as compared to the control, respectively. All heavy metals content, except cadmium, nickel and zinc, in corn grain were not significantly different from the control. Arsenic, cadmium and zinc in corn grain were strongly positively correlated with concentrations in soil. The heavy metal content in corn grain was within regulated limits for human consumption.

Unique zinc mass in mandibles separates drywood termites from other groups of termites.

Previously, the presence of metals in arthropod mandibles has been linked with harder cuticle, and in termites, a 20% increase in hardness has been found for mandibles containing major quantities of zinc. The current study utilises electron microscopy and energy-dispersive X-ray microanalysis to assess incidence and abundance of metals in all extant subfamilies of the Isoptera. The basal clades contain no zinc and little to no manganese in the cutting edge of the mandible cuticle, suggesting that these states are ancestral for termites. However, experimentation with mandibles in vitro indicates the presence of some elements of the cuticular biochemistry necessary to enable uptake of zinc. The Termopsidae, Serritermitidae, Rhinotermitidae and Termitidae all contain minor quantities of manganese, while trace to minor quantities of zinc occur in all except the Serritermitidae. In contrast, all Kalotermitidae or drywood termites contain major levels of zinc in the mandible edge. Diet and life type are explored as links to metal profiles across the termites. The presence of harder mandibles in the drywood termites may be related to lack of access to free water with which to moisten wood. Scratch tests were applied to a set of mandibles. The coefficient of friction for Cryptotermes primus (Kalotermitidae) mandibles, when compared with species from other subfamilies, indicates that zinc-containing mandibles are likely to be more scratch resistant.

Insect mandibles--comparative mechanical properties and links with metal incorporation.

A number of arthropod taxa contain metals in their mandibles (jaws), such as zinc, manganese, iron, and calcium. The occurrence of zinc and its co-located halogen chlorine have been studied in relation to the mechanical properties and shown to be linked in a direct fashion with increasing concentration. Hardness along with elastic modulus (stiffness) has also been linked to zinc and halogen concentration in some marine polychaete worms. The metal appears to be incorporated within the biological matrix, possibly bonding with proteins. However, the comparative advantage of metal inclusion has not been tested. It is possible that without metals, alternative mechanisms are used to achieve hardness of equal value in similar 'tools' such as mandibles. This question has direct bearing on the significance of metal hardening. In the present article, we compare across mandibles from six termite species, including samples with major zinc concentration, minor manganese, and no metals. Nanoindentation, electron microscopy, and electron microanalysis are used to assess metal concentration, form, and mechanical properties. The data demonstrate that termite mandibles lacking metals when fully developed have lower values for hardness and elastic modulus. Zinc is linked to a relative 20% increase in hardness when compared with mandibles devoid of metals. The similar transition metal, manganese, found in minor concentrations, is not linked to any significant increase in these mechanical properties. This raises the question of the function of manganese, which is as commonly found in insect mandibles as zinc and often located in the same mandibles.