Insights on hazardous metal bioaccessibility, and groundwater impacted by Zn residues from a legacy mine and risk evaluation of adjacent soils.

This study explored the legacy impact of Zinc plant residues (ZPRs) in Kabwe, Zambia, on the environment and human health, particularly in light of the town's reputation for Pb pollution. ZPRs solid samples and groundwater within and around ZPRs zone were collected from the legacy mine, along with soils in a 10 km radius from the mine site. Bioaccessible fractions of Pb and Zn were elucidated by Japanese leaching test (JLT) and simple bioaccessibility extraction test (SBET). Cationic speciation of Pb and Zn from inhalable and ingestible ZPRs particles was investigated via sequential extraction. Groundwater in the ZPRs area showed higher Zn levels (1490 mg/L) compared to Pb (1.7 mg/L). Elevated Zn concentration were facilitated by the presence of soluble Zn sulfates while Pb was constrained due to its precipitation as anglesite. Groundwater sampled outside the ZPRs area was within the Zambia regulatory limits (< 0.5 mg/L for Pb and < 1 mg/L for Zn). Inhalation exposure to < 30 µm dust particles from ZPRs and soils near the mine indicated negligible risk, with < 3% of bioaccessible Pb in artificial lysosomal fluid. Meanwhile, oral intake of ZPRs particles < 250 µm revealed elevated bioaccessible fractions (36% for Pb and 70% for Zn). ZPRs cationic speciation of ingestible particles < 30 µm, 30-75 µm, 75-150 µm and 150-250 µm indicated that the bioaccessible Pb predominantly emanated from labile Pb fractions under gastric conditions with pH < 1. This was due to the dissolution of Pb associated with the exchangeable phase, carbonates and iron/manganese oxides; however, only exchangeable/carbonate Pb was bioaccessible at pH < 2. Hazard quotients indicated increased risks of Pb intoxication through the ingestion of ZPRs and soils near the legacy mine, with higher risks observed in children, emphasizing the need to remediate legacy mine wastes to reduce health risks and protect groundwater through monitoring in mining-affected regions.

Determination and risk assessment of heavy metals in raw foodstuffs sold from open markets in Zambia; a comparison of Kabwe, Kitwe, and Lusaka towns.

The research focused on risk assessment of some heavy metals in common vegetables and fish sold on open markets in three towns of Zambia. The mean level of heavy metals ranged as follows (mg/kg): 1.9 to 662.7, 3.0 to 3472.3 and 2.0 to 1698.7 of cadmium (lowest) and aluminium (highest) for samples from Kabwe, Kitwe and Lusaka, respectively. Statistical analysis indicated that the concentrations of samples from Kitwe and Lusaka towns were similar, P > 0.05. However, there were noteworthy differences in the mean amounts of heavy metals in samples from Kitwe and Kabwe, and samples from Kabwe and Lusaka towns, P < .0167. The health risk analysis indicates possible non-carcinogenic and carcinogenic risks to the consumer. This is because the hazard index (HI) for all metals in all samples from all towns was greater than 1 and the cancer risk (CR) for cadmium was above 10-4 in all samples from all towns.

Dye tracing of the Lusaka karstified aquifer system: implications towards urban groundwater quality protection.

Management of groundwater resources requires a large amount of data, coupled with an understanding of the aquifer system behavior. In developing countries, the scarcity in groundwater data has led to aquifers being managed according to rule-of-thumb standards or even abandoned as unmanageable at times. Groundwater quality protection thus has been through prescribed separation distances often without due regard for internal and boundary characteristics that affect response rates of groundwater movement, attenuation of pollutants, and recharge. In this study, we examine the boundary characteristics of the highly vulnerable karst aquifer system in the rapidly expanding city of Lusaka using a dye tracer technique. We investigate the flow dynamics (magnitude and direction) of groundwater using dye tracer dyes (fluorescein and rhodamine) spiked in pit latrines and observed at discharge springs. The results provide irrefutable evidence that pit latrines are a source and a pathway to contamination of groundwater. Dye tracer movement in groundwater was rapid, estimated at 340 and 430 m/day for fluorescein and rhodamine, respectively, through interconnected conduit density. The vadose zone (epikarst) tends to store diffuse recharge before release to the phreatic zone. These rapid groundwater movements render regulatory separation minimum distances of 30 m between abstraction wells and pit latrines/septic tanks in such environments to be an ineffective means of reducing contamination. The policy focus in the protection of groundwater quality should henceforth be on robust sanitation solutions especially for low-income communities that recognize the socio-economic diversity.

Smelter-derived soil contamination in Luanshya, Zambia.

Extensive mining and smelting contributed to the declining quality of Luanshya soils. The local smelter was the epicenter of contamination as shown by a spatial distribution analysis. Closeby soil profiles smelter exhibit extremely high Cu concentrations (up to 46,000 mg kg-1 Cu) relative to deeper layers where only background levels of trace elements were observed. A remote profile did not exhibit significant contamination. Lead isotopic ratios revealed that Pb contamination in the Luanshya soils was not smelter-derived. It was shown in this way that the historical usage of leaded gasoline was the main source of this metal. Although the Luanshya smelter also produced Co, this metal was not an important contaminant. Copper leaching was a concern in Luanshya. Upwards of 52 % of Cu was extractable in the exchangeable step of a sequential extraction procedure (SEP), but only for samples where Cu concentrations were high, suggesting that Cu was released exclusively from anthropogenic particles. This was supported by the SEP results for similar depths at the remote soil, where only a small fraction of Cu was labile (5.6 %). Lead and Co were strongly bound in the soils throughout. The excess of Cu in the topsoils was mostly bound in smelter-derived particles. These appeared as spherical fast-cooled droplets composed mostly of sulfides, oxides, and glass. X-ray diffraction and electron probe microanalysis of those particles allowed for a phase classification. Compositions were regularly not stoichiometric so most particles were classified as intermediate solid solutions. However, molecular proportions often closely resembled those of bornite, chalcanthite, cuprospinel, covellite, delafossite, diginite, or hydrous ferric oxides. Concentrations of Cu were often 100 % near the center of the particles indicating an inefficient smelting process. Weathering to some degree was common, which in conjunction with the susceptibility of Cu leaching was highly alarming.

Detection of Escherichia coli, rotavirus, and Cryptosporidium spp. from drinking water, kitchenware, and flies in a periurban community of Lusaka, Zambia.

Fecal contamination with a poor water, sanitation and hygiene environment in urban informal settlements poses diarrhea risks. Little information is available on the contamination of environmental media with enteric pathogens in such settlements. We investigated the contamination of Escherichia coli, rotavirus, and Cryptosporidium spp. in water, on kitchenware, and on flies in urban informal settlements of Chawama and Kanyama, Lusaka, Zambia. These environmental media were examined by XM-G agar cultivation for E. coli and specific real-time RT-PCR assays to detect rotavirus and Cryptosporidium spp. E. coli; rotavirus, and Cryptosporidium spp. were detected in samples of household stored drinking water (6 of 10 samples, 3 of 10 samples, and 2 of 10 samples, respectively), cups (10 of 20 samples, 2 of 13 samples, 1 of 13 samples, respectively), and flies (35 of 55 samples, 5 of 17 samples, 1 of 17 samples, respectively). The ranges of rotavirus concentrations in household stored drinking water, on cups, and flies were 2.9 × 102-2.2 × 105 copies/L, 1.2 × 102-4.3 × 102 copies/cup, and 5.0 × 101-2.0 × 102 copies/fly, respectively. These results indicate the contribution of drinking water and kitchenware to enteric pathogen exposure and potential role of flies in microbial transmission.

Solid-Phase Partitioning and Leaching Behavior of Pb and Zn from Playground Soils in Kabwe, Zambia.

Zambia's Kabwe mine wastes (KMWs) are responsible for contaminating the surrounding soil and dust in the Kabwe district. Unfortunately, these wastes arise from the historical mining activities of lead (Pb) and Zinc (Zn), which lacked adequate waste management strategies. As a result, potentially toxic elements (PTEs) (Pb and Zn) spread across the Kabwe district. To assess the soil pollution derived from previous mining activities, we studied topsoil samples (n = 8) from the school playground soils (SPs). In this study, the degree of contamination, geochemical partitioning, and leachability, coupled with the release and retention of Pb and Zn, were studied. The SPs were classified as extremely enriched (EF > 40) and contaminated with Pb (Igeo > 5). On average, Pb (up to 89%) and Zn (up to 69%) were bound with exchangeable, weak acid-soluble, reducible and oxidizable phases, which are considered as 'geochemically mobile' phases in the environment. The leachates from the soils (n = 5) exceeded the Zambian standard (ZS: 190:2010) for Pb in potable drinking water (Pb < 0.01 mg/L). Furthermore, the spatial distribution of Pb and Zn showed a significant reduction in contents of Pb and Zn with the distance from the mine area.

Anthropogenic influences on Zambian water quality: hydropower and land-use change.

The Zambezi River Basin in Southern Africa is undergoing rapid development and population growth. Agricultural intensification, urbanization and future development of hydropower dams will likely lead to a degradation of surface water quality, but there have been few formal assessments of where, how and why these changes impact specific water quality parameters based on in situ data spanning a large region. We sampled a large suite of biogeochemical water quality parameters at 14 locations in four field campaigns in central and southern Zambia in 2018 and 2019 to characterize seasonal changes in water quality in response to large hydropower dams and human landscape transformations. We find that the major rivers (Zambezi and Kafue) are very clean with extremely low concentrations of solutes, but suffer from thermal changes, hypoxia and loss of suspended sediment below dams. Smaller tributaries with a relatively large anthropogenic landcover footprint in their catchments show signs of pollution in the form of higher concentrations of nutrients and dissolved ions. We find significant relationships between crop and urban land cover metrics and selected water quality metrics (i.e. conductivity, phosphorus and nitrogen) across our data set. These results reflect a very high-quality waterscape exhibiting some hotspots of degradation associated with specific human activities. We anticipate that as agricultural intensification, urbanization and future hydropower development continue to accelerate in the basin, the number and extent of these hotspots of water quality degradation will grow in response. There is an opportunity for governments, managers and industry to mitigate water quality degradation via investment in sustainable infrastructure and practice, such as wastewater treatment, environmental dam operations, or riparian protection zones.

Drinking Water Quality and Provision in Six Low-Income, Peri-Urban Communities of Lusaka, Zambia.

Lusaka, Zambia, is a rapidly growing city located on a vulnerable karstic dolomite aquifer that provides most of the city's drinking water. Over 65% of residents live in peri-urban communities with inadequate sanitation leading to widespread groundwater contamination and the spread of waterborne diseases such as cholera. To fill the water service gap, Water Trusts were created: public/private partnerships designed to provide clean water to peri-urban community residents. Water Trusts extract groundwater via boreholes, treat it with chlorine, and distribute it to residents via public kiosks. We investigated the efficacy of drinking water provision to residents in six of Lusaka's peri-urban communities with Water Trusts. Water samples were collected from Water Trust boreholes and kiosks, privately owned boreholes, and shallow wells during four sampling efforts. To assess potential risk to human health, water samples were analyzed for Escherichia coli (E. coli) and nitrate. Shallow wells were significantly more contaminated with E. coli than Water Trust boreholes, kiosks, and private boreholes (Tukey-adjusted p values of 9.9 × 10-6). Shallow wells and private boreholes had significantly higher nitrate-N concentrations (mean of 29.6 mg/L) than the Water Trust boreholes and kiosks (mean of 8.8 mg/L) (p value = 1.1 × 10-4). In 2016, a questionnaire was distributed to Water Trust managers to assess their ability to meet demands. In the six communities studied, Water Trusts served only about 60% of their residents. Water Trusts provide a much safer alternative to shallow wells with respect to nitrate and E. coli, but they struggle to keep pace with growing demand.

Geochemical behaviour of heavy metals in sludge effluents and solid deposits on the Zambian Copperbelt: Implication for effluent treatment and sludge reuse.

Sludge effluents and solid deposits generated from the conventional lime treatment processes on the Zambian Copperbelt have led to reports of copper (Cu) and cobalt (Co) contamination into the nearby water bodies. To better understand the behaviour of the metals; partitioning, adsorption and their specific binding forms were studied through sequential extraction, batch adsorption experiments and surface complexation modeling (SCM). Results of mineral composition analyses indicated that micas, kaolinite, quartz and feldspar are abundant with hydrous ferric oxide (HFO) precipitates that formed as a result of the weathering of biotite grains existing as grain surface coating. Sequential extractionrevealed that Cu and Co metals are partitioned in the order of: exchangeable (F1: 600-1500 mg/kg Cu; 100-200 mg/kg Co), acid-soluble (F2: 2200-5500 mg/kg Cu; 190-220 mg/kg Co) and reducible fraction (F3: 2200-5500 mg/kg Cu; 260-300 mg/kg Co). Metals in F1 are hosted by kaolinite, F2 by both kaolinite and HFO whereas in F3 by dominantly HFO. Equal Cu concentration between F2 and F3 is due to both the limited amount of HFO (i.e. 5-10 g/kg) and desorption of loosely adsorbed Cu and Co metals to HFO surfaces. Batch adsorption experiments revealed adsorption as the dominant metal retention mechanism. According to modeling predictions, HFO sites are the dominant metal adsorption sites. At HFO site; >(s)FeOCo+, Co showed adsorption decrease from 40% in single system to 25% in binary system between pH 7 - 7.5 due to metal competition for adsorption sites. The high Cu concentration (i.e. 0.5-1.1% Cu) displaced low Co (i.e. 0.03-0.07% Co) concentration from the adsorption sites present in sludge, thus rendering Co mobile into the environment. To keep the adsorbed metals stable from release, optimal pH of 7.5 is suggested during treatment with lime. At this optimal pH, metals are decreased to below the regulation standard values and with less generation of voluminous sludge. Adsorbed Cu and Co can be recoverable from sludge through acid treatment at pH <3 based on sequential extraction results. The resultant metal-free sludge material has potential of been used as aggregate in construction.

Biosorption of Pb (II) and Zn (II) from aqueous solution by Oceanobacillus profundus isolated from an abandoned mine.

The present study investigated biosorption of Pb (II) and Zn (II) using a heavy metal tolerant bacterium Oceanobacillus profundus KBZ 3-2 isolated from a contaminated site. The effects of process parameters such as effect on bacterial growth, pH and initial lead ion concentration were studied. The results showed that the maximum removal percentage for Pb (II) was 97% at an initial concentration of 50 mg/L whereas maximum removal percentage for Zn (II) was at 54% at an initial concentration of 2 mg/L obtained at pH 6 and 30 °C. The isolated bacteria were found to sequester both Pb (II) and Zn (II) in the extracellular polymeric substance (EPS). The EPS facilitates ion exchange and metal chelation-complexation by virtue of the existence of ionizable functional groups such as carboxyl, sulfate, and phosphate present in the protein and polysaccharides. Therefore, the use of indigenous bacteria in the remediation of contaminated water is an eco-friendly way of solving anthropogenic contamination.

Potential of aquatic weeds to improve water quality in natural waterways of the Zambezi catchment.

One prominent effect of nutrient pollution of surface waters is the mass invasion of floating plants, which can clog waterways, disrupting human use of aquatic systems. These plants are widely vilified and motivate expensive control campaigns, but their presence may be providing a poorly recognized function in the cycling of excess nutrients. The capacity for floating plants to absorb nutrients from surface water has been understood for decades, primarily from their use in constructed wetlands for wastewater treatment. Yet, in natural settings, there has not been to date any effort to quantify whether floating plant invasions represent important pools or fluxes of nutrients relative to those of the river catchments in which they occur. We found that seasonal hydrologic cycles in the Zambezi trap and flush floating plants from river choke points, such as dams and river confluences, on an annual basis. Peak plant biomass at such choke points constitutes a proxy for estimating annual plant-bound nutrient loads. We assessed the significance of floating vegetation as nutrient sinks by comparing annual plant-bound nutrient loading to conventional river nutrient loading (dissolved and particulate) for four tributaries of the Zambezi River in Zambia. We found that the relative importance of floating vegetation was greatest in the more urbanized catchments, such as the Maramba River draining the city of Livingstone, representing approximately 30% and 9% of annual digestible phosphorus and nitrogen flux respectively. We also found plant-bound phosphorus to be important in the Kafue River (19%), draining the industrial town of Kafue and extensive sugarcane plantations. These results demonstrate the great potential of floating plants to take up excess nutrients from natural river systems. Given the importance of hydrology in the life cycle of floating vegetation, controlled dam discharges may have an important role in managing them and their water quality treatment functions.

Slag dusts from Kabwe (Zambia): Contaminant mineralogy and oral bioaccessibility.

The former Pb-Zn mining town of Kabwe in central Zambia is ranked amongst the worst polluted areas both in Africa and in the world. The fine dust particles from the ISF and Waelz slags deposited in Kabwe represent a health risk for the local population. Here, we combined a detailed multi-method mineralogical investigation with oral bioaccessibility testing in simulated gastric fluid (SGF; 0.4 M glycine, pH 1.5, L/S ratio of 100, 1 h, 37 °C) to evaluate the risk related to the incidental dust ingestion. The slag dust fractions contain up to 2610 mg/kg V, 6.3 wt% Pb and 19 wt% Zn. The metals are mainly bound in a slag glass and secondary phases, which formed during the slag weathering or were windblown from nearby tailing stockpiles (carbonates, Fe and Mn oxides, phosphates, vanadates). The bioaccessible fractions (BAFs) are rather high for all the main contaminants, with the BAF values generally higher for the ISF slags than for the Waelz slags: Pb (24-96%), V (21-100%) and Zn (54-81%). The results clearly indicate the potential risks related to the incidental slag dust ingestion. Even when a conservative value of the dust daily intake (100 mg/day) is considered, the daily contaminant intake significantly exceeds the tolerable daily intake limits, especially for Pb â‰« V > Zn. At higher ingestion rates, other minor contaminants (As, Cd) also become a health risk, especially for children. The slag heaps in Kabwe should be fenced to prevent local people entering and should be covered to limit the dust dispersion.

Sixty years since the creation of Lake Kariba: Thermal and oxygen dynamics in the riverine and lacustrine sub-basins.

The current boom of dam construction at low latitudes endangers the integrity and function of major tropical river systems. A deeper understanding of the physical and chemical functioning of tropical reservoirs is essential to mitigate dam-related impacts. However, the development of predictive tools is hampered by a lack of consistent data on physical mixing and biogeochemistry of tropical reservoirs. In this study, we focus on Lake Kariba (Southern Africa), the largest artificial lake in the world by volume. Kariba Dam forms a transboundary reservoir between Zambia and Zimbabwe, and therefore its management represents a socio-politically sensitive issue because the Kariba Dam operation completely changed the downstream hydrological regime. Although Lake Kariba represents a unique and scientifically interesting case study, there is no consistent dataset documenting its physical and chemical behaviour over time. This limits the scope for quantitative studies of this reservoir and its downstream impacts. To address this research gap, we aggregated a consistent database of in situ measurements of temperature and oxygen depth profiles for the entire 60 years of Lake Kariba's lifetime and performed a detailed statistical analysis of the thermal and oxygen regime of the artificial lake to classify the different behaviours of the lake's sub-basins. We demonstrate that the seasonal stratification strongly depends on the depth of the water column and on the distance from the lake inflow. Satellite data confirm these spatiotemporal variations in surface temperature, and reveal a consistent longitudinal warming trend of the lake surface water temperature of about 1.5°C from the inflow to the dam. Finally, our results suggest that the stratification dynamics of the lacustrine sub-basins have the potential to alter the downstream Zambezi water quality. Future research should focus on assessing such alterations and developing strategies to mitigate them.

Efficacy of biocementation of lead mine waste from the Kabwe Mine site evaluated using Pararhodobacter sp.

Biocementation of hazardous waste is used in reducing the mobility of contaminants, but studies on evaluating its efficacy have not been well documented. Therefore, to evaluate the efficacy of this method, physicochemical factors affecting stabilized hazardous products of in situ microbially induced calcium carbonate precipitation (MICP) were determined. The strength and leach resistance were investigated using the bacterium Pararhodobacter sp. Pb-contaminated kiln slag (KS) and leach plant residue (LPR) collected from Kabwe, Zambia, were investigated. Biocemented KS and KS/LPR had leachate Pb concentrations below the detection limit of < 0.001 mg/L, resisted slaking, and had maximum unconfined compressive strengths of 8 MPa for KS and 4 MPa for KS/LPR. Furthermore, biocemented KS and KS/LPR exhibited lower water absorption coefficient values, which could potentially reduce the water transportation of Pb2+. The results of this study show that MICP can reduce Pb2+ mobility in mine wastes. The improved physicochemical properties of the biocemented materials, therefore, indicates that this technique is an effective tool in stabilizing hazardous mine wastes and, consequently, preventing water and soil contamination.

Solidification of sand by Pb(II)-tolerant bacteria for capping mine waste to control metallic dust: Case of the abandoned Kabwe Mine, Zambia.

Environmental impacts resulting from historic lead and zinc mining in Kabwe, Zambia affect human health due to the dust generated from the mine waste that contains lead, a known hazardous pollutant. We employed microbially induced calcium carbonate precipitation (MICP), an alternative capping method, to prevent dust generation and reduce the mobility of contaminants. Pb-resistant Oceanobacillus profundus KBZ 1-3 and O. profundus KBZ 2-5 isolated from Kabwe were used to biocement the sand that would act as a cover to prevent dust and water infiltration. Sand biocemented by KBZ 1-3 and KBZ 2-5 had maximum unconfined compressive strength values of 3.2 MPa and 5.5 MPa, respectively. Additionally, biocemented sand exhibited reduced water permeability values of 9.6 × 10-8 m/s and 8.9 × 10-8 m/s for O. profundus KBZ 1-3 and KBZ 2-5, respectively, which could potentially limit the entrance of water and oxygen into the dump, hence reducing the leaching of heavy metals. We propose that these isolates represent an option for bioremediating contaminated waste by preventing both metallic dust from becoming airborne and rainwater from infiltrating into the waste. O. profundus KBZ 1-3 and O. profundus KBZ 2-5 isolated form Kabwe represent a novel species that has, for the first time, been applied in a bioremediation study.

The impact of wetland on neutral mine drainage from mining wastes at Luanshya in the Zambian Copperbelt in the framework of climate change.

The impact of a natural wetland ("dambo" in Zambia) on neutral mine drainage at Luanshya in the Zambian Copperbelt has been investigated during an intermediate discharge period (July) using a multi-method characterization of solid phase samples, sequential extraction analysis, X-ray diffraction, Mössbauer spectroscopy, and scanning electron microscopy combined with water analyses, isotopic analyses, and geochemical modeling. In the wetland, the principal identified solid phases in sediments were carbonates, gypsum, and ferric oxyhydroxides. A significant portion of the ochres was present as insoluble hematite. Mine drainage pH values decrease, and log [Formula: see text] values increase after inflow of water into the wetland; dissolved and suspended concentrations of Fe, Mn, Cu, and Co also decrease. Based on speciation calculations, there is no precipitation of secondary Cu and Co minerals in the period of sampling, but it can occur later in dry period when the flow rate is reduced. Concentrations of sulfate decrease, and values of δ34S(SO4) in the wetland increase in parallel, suggesting sulfate reduction is occurring. In more advanced dry period, the discharge in mine drainage stream is probably much lower and water can reach supersaturation with respect to minerals such as gypsum, which has been found in sediments. Wetlands have a positive impact on mine drainage water quality due to the removal of metals by adsorption, co-precipitation, and filtration of colloids. However, there can also be a rebound of contamination by seepage inflow downstream from the wetland. Ongoing climate change with extreme hydrologic events may enhance differences between dry and rainy seasons with resulting faster mobilization of contaminants.

Copper isotopic record in soils and tree rings near a copper smelter, Copperbelt, Zambia.

The copper (Cu) content and isotopic composition were studied in soils and in pine tree rings at locations close to and far from the Cu smelter, located at Kitwe, Zambia. The soil in the remote area contained 25-75mgkg-1 Cu, whereas the soil close to the smelter contained 207-44,000mgkg-1 Cu. The δ65Cu at the remote area and close to the smelter varied in the range -0.40 to -0.11‰, and -0.44 to 0.01‰ respectively. The δ65Cu of the surface soil at both profiles (-0.44 to -0.40‰) is similar to the isotopic composition of the concentrates processed in the smelter (-0.75 to -0.45‰), i.e. both locations are affected by Cu ore dust. The increase in the δ65Cu in the direction towards the centre of the profile is caused by the oxidative dissolution of Cu(I) from ore minerals, during which heavier Cu is released. In deeper parts of the profile, there is a slight decrease in δ65Cu because of easier mobilisation of the lighter isotope. The tree rings at the two locations differ in the total contents and isotopic composition. At the less contaminated site, the Cu contents equal 0.4 to 1.1mgkg-1 while, at the polluted site, the Cu contents vary in the range 3 to 47mgkg-1. Whereas, at the less contaminated location, the tree rings are substantially enriched in lighter Cu (δ65Cu=-0.76 to -2.2‰), at locations close to the smelter the tree rings have an isotopic composition (-0.31 to -0.88‰) similar to that of the contaminated soil or processed ore. The isotopic compositions of the tree rings close to the smelter are affected particularly by interception of dust containing Cu ore. The δ13C in tree rings demonstrate the interconnection of acidification and Cu mobility.

Composition and fate of mine- and smelter-derived particles in soils of humid subtropical and hot semi-arid areas.

We studied the heavy mineral fraction, separated from mining- and smelter-affected topsoils, from both a humid subtropical area (Mufulira, Zambian Copperbelt) and a hot semi-arid area (Tsumeb, Namibia). High concentrations of metal(loid)s were detected in the studied soils: up to 1450mgAskg(-1), 8980mgCukg(-1), 4640mgPbkg(-1), 2620mgZnkg(-1). A combination of X-ray diffraction analysis (XRD), scanning electron microscopy (SEM/EDS), and electron probe microanalysis (EPMA) helped to identify the phases forming individual metal(loid)-bearing particles. Whereas spherical particles originate from the smelting and flue gas cleaning processes, angular particles have either geogenic origins or they are windblown from the mining operations and mine waste disposal sites. Sulphides from ores and mine tailings often exhibit weathering rims in contrast to smelter-derived high-temperature sulphides (chalcocite [Cu2S], digenite [Cu9S5], covellite [CuS], non-stoichiometric quenched Cu-Fe-S phases). Soils from humid subtropical areas exhibit higher available concentrations of metal(loids), and higher frequencies of weathering features (especially for copper-bearing oxides such as delafossite [Cu(1+)Fe(3+)O2]) are observed. In contrast, metal(loid)s are efficiently retained in semi-arid soils, where a high proportion of non-weathered smelter slag particles and low-solubility Ca-Cu-Pb arsenates occur. Our results indicate that compared to semi-arid areas (where inorganic contaminants were rather immobile in soils despite their high concentrations) a higher potential risk exists for agriculture in mine- and smelter-affected humid subtropical areas (where metal(loid) contaminants can be highly available for the uptake by crops).

Surprisingly contrasting metal distribution and fractionation patterns in copper smelter-affected tropical soils in forested and grassland areas (Mufulira, Zambian Copperbelt).

Six soil profiles located near Mufulira (Zambian Copperbelt) were studied to evaluate and compare the extent of environmental pollution of Cu-ore mining and smelting in both forested and grassland areas. The highest metal concentrations were detected in the uppermost soil layers with the following maxima: Co 45.8 mg kg(-1), Cu 8,980 mg kg(-1), Pb 41.6 mg kg(-1), and Zn 97.0 mg kg(-1). Numerous anthropogenic metal-bearing particles were detected in the most polluted soil layers. The spherical smelter-derived particles were mainly composed of covellite (CuS) and chalcocite (Cu2S), while the angular mining-derived particles were mostly composed of chalcopyrite (CuFeS2). Additionally, Fe-Cu oxide particles predominantly corresponding to tenorite (CuO) and delafossite (Cu(1+)Fe(3+)O2), along with hydrated Fe-oxides corresponding to secondary weathering products, were detected. In contrast to smelter-affected soils in temperate climates, where forest soils are significantly more enriched in metals than tilled soils due to high canopy interception, our data indicate a higher proportion of metal-bearing anthropogenic particles and higher metal concentrations in soils from unforested sites. This phenomenon is probably related to the more frequent and intense bushfires in forested areas, leading to the mobilization of pollutants contained in the biomass-rich surface soils back into the atmosphere.

The extent of arsenic and of metal uptake by aboveground tissues of Pteris vittata and Cyperus involucratus growing in copper- and cobalt-rich tailings of the Zambian copperbelt.

The extent of arsenic (As) and metal accumulation in fronds of the As hyperaccumulator Pteris vittata (Chinese brake fern) and in leaves of Cyperus involucratus, which grow on the surface of an old flotation tailings pond in the Zambian Copperbelt province, was studied. The tailings consist of two types of material with distinct chemical composition: (1) reddish-brown tailings rich in As, iron (Fe), and other metals, and (2) grey-green tailings with a lower content of As, Fe, and other metals, apart from manganese (Mn). P. vittata accumulates from 2350 to 5018 µg g(-1) As (total dry weight [dw]) in its fronds regardless of different total and plant-available As concentrations in both types of tailings. Concentrations of As in C. involucratus leaves are much lower (0.24-30.3 µg g(-1) dw). Contents of copper (Cu) and cobalt (Co) in fronds of P. vittata (151-237 and 18-38 µg g(-1) dw, respectively) and in leaves of C. involucratus (96-151 and 9-14 µg g(-1) dw, respectively) are high, whereas concentrations of other metals (Fe, Mn, and zinc [Zn]) are low and comparable with contents of the given metals in common plants. Despite great differences in metal concentrations in the two types of deposited materials, concentrations of most metals in plant tissues are very similar. This indicates an exclusion or avoidance mechanism operating when concentrations of the metals in substrate are particularly high. The results of the investigation show that Chinese brake fern is not only a hyperaccumulator of As but has adapted itself to high concentrations of Cu and Co in flotation tailings of the Zambian Copperbelt.