The influence of the scale of mining activity and mine site remediation on the contamination legacy of historical metal mining activity

Globally, thousands of kilometres of rivers are degraded due to the presence of elevated concentrations of potentially harmful elements (PHEs) sourced from historical metal mining activity. In many countries, the presence of contaminated water and river sediment creates a legal requirement to address such problems. Remediation of mining-associated point sources has often been focused upon improving river water quality; however, this study evaluates the contaminant legacy present within river sediments and attempts to assess the influence of the scale of mining activity and post-mining remediation upon the magnitude of PHE contamination found within contemporary river sediments. Data collected from four exemplar catchments indicates a strong relationship between the scale of historical mining, as measured by ore output, and maximum PHE enrichment factors, calculated versus environmental quality guidelines. The use of channel slope as a proxy measure for the degree of channel-floodplain coupling indicates that enrichment factors for PHEs in contemporary river sediments may also be the highest where channel-floodplain coupling is the greatest. Calculation of a metric score for mine remediation activity indicates no clear influence of the scale of remediation activity and PHE enrichment factors for river sediments. It is suggested that whilst exemplars of significant successes at improving post-remediation river water quality can be identified; river sediment quality is a much more long-lasting environmental problem. In addition, it is suggested that improvements to river sediment quality do not occur quickly or easily as a result of remediation actions focused a specific mining point sources. Data indicate that PHEs continue to be episodically dispersed through river catchments hundreds of years after the cessation of mining activity, especially during flood flows. The high PHE loads of flood sediments in mining-affected river catchments and the predicted changes to flood frequency, especially, in many river catchments, provides further evidence of the need to enact effective mine remediation strategies and to fully consider the role of river sediments in prolonging the environmental legacy of historical mine sites.     

Depth-dependence and monthly variability of charophyte biomass production: consequences for the precipitation of calcium carbonate in a shallow <Emphasis Type="Italic">Chara</Emphasis>-lake

The month-to-month variability of biomass and CaCO₃ precipitation by dense charophyte beds was studied in a shallow Chara-lake at two depths, 1 and 3 m. Charophyte dry weights (d.w.), the percentage contribution of calcium carbonate to the dry weight and the precipitation of CaCO₃ per 1 m² were analysed from May to October 2011. Physical-chemical parameters of water were also measured for the same sample locations. The mean dry weight and calcium carbonate precipitation were significantly higher at 1 m than at 3 m. The highest measured charophyte dry weight (exceeding 2000 g m^?2) was noted at 1 m depth in September, and the highest CaCO₃ content in the d.w. (exceeding 80 % of d.w.) was observed at 3 m depth in August. The highest CaCO₃ precipitation per 1 m² exceeded 1695 g at 1 m depth in August. Significant differences in photosynthetically active radiation (PAR) were found between 1 and 3 m depths; there were no significant differences between depths for other water properties. At both sampling depths, there were distinct correlations between the d.w., CaCO₃ content and precipitation and water properties. In addition to PAR, the water temperature and magnesium and calcium ion concentrations were among the most significant determinants of CaCO₃ content and d.w. The results show that light availability seems to be the major factor in determining charophyte biomass in a typical, undisturbed Chara-lake. The study results are discussed in light of the role of charophyte vegetation in whole ecosystem functioning, with a particular focus on sedimentary processes and the biogeochemical cycle within the littoral zone.     

Assessment of trace metal air pollution in Paris using slurry-TXRF analysis on cemetery mosses

Mosses are useful, ubiquitous accumulation biomonitors and as such can be used for biomonitoring surveys. However, the biomonitoring of atmospheric pollution can be compromised in urban contexts if the targeted biomonitors are regularly disturbed, irregularly distributed, or are difficult to access. Here, we test the hypothesis that cemeteries are appropriate moss sampling sites for the evaluation of air pollution in urban areas. We sampled mosses growing on gravestones in 21 urban and peri-urban cemeteries in the Paris metropolitan area. We focused on Grimmia pulvinata (Hedwig) Smith, a species abundantly found in all studied cemeteries and very common in Europe. The concentration of Al, As, Br, Ca, Ce, Cl, Cr, Cu, Fe, K, Mn, Ni, V, P, Pb, Rb, S, Sr, Ti, and Zn was determined by a total reflection X-ray fluorescence technique coupled with a slurry sampling method (slurry-TXRF). This method avoids a digestion step, reduces the risk of sample contamination, and works even at low sample quantities. Elemental markers of road traffic indicated that the highest polluted cemeteries were located near the highly frequented Parisian ring road and under the influence of prevailing winds. The sites with the lowest pollution were found not only in the peri-urban cemeteries, adjoining forest or farming landscapes, but also in the large and relatively wooded cemeteries located in the center of Paris. Our results suggest that (1) slurry-TXRF might be successfully used with moss material, (2) G. pulvinata might be a good biomonitor of trace metals air pollution in urban context, and (3) cemetery moss sampling could be a useful complement for monitoring urban areas.

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Graphical abstract We tested the hypothesis that cemeteries are appropriate moss sampling sites for the evaluation of air pollution in urban areas. We sampled 110 moss cushions (Grimmia pulvinata) growing on gravestones in 21 urban and peri-urban cemeteries in the Paris metropolitan area. The concentration of 20 elements in mosses was determined by a total reflection X-ray fluorescence technique coupled with a slurry sampling method. Statistical analysis revealed that: - Urbanized Parisian areas crossed by traffic roads have the highest polluted cemeteries with a strong influence of main wind direction on the distribution of air pollutants - As expected, small cemeteries with low tree density were heavily polluted - Less obvious, large green spaces such as large cemeteries (Père Lachaise, Montmartre, Montparnasse) in the center of a dense metropolis like Paris present the same level of atmospheric trace metal pollution as cemeteries in less urbanized areas or nearing a very large forest. This suggests that even in densely urbanized areas, there is more spatial variability in pollution distribution than usually assumed and that large urban areas with low traffic and green filters such as trees are likely to intercept air pollutants

     

Research and application of method of oxygen isotope of inorganic phosphate in Beijing agricultural soils

Phosphorus (P) in agricultural ecosystems is an essential and limited element for plants and microorganisms. However, environmental problems caused by P accumulation as well as by P loss have become more and more serious. Oxygen isotopes of phosphate can trace the sources, migration, and transformation of P in agricultural soils. In order to use the isotopes of phosphate oxygen, appropriate extraction and purification methods for inorganic phosphate from soils are necessary. Here, we combined two different methods to analyze the oxygen isotopic composition of inorganic phosphate (δ¹⁸O_P) from chemical fertilizers and different fractions (Milli-Q water, 0.5 mol L^?1 NaHCO₃ (pH = 8.5), 0.1 mol L^?1 NaOH and 1 mol L^?1 HCl) of agricultural soils from the Beijing area. The δ¹⁸O_P results of the water extracts and NaHCO₃ extracts in most samples were close to the calculated equilibrium value. These phenomena can be explained by rapid P cycling in soils and the influence of chemical fertilizers. The δ¹⁸O_P value of the water extracts and NaHCO₃ extracts in some soil samples below the equilibrium value may be caused by the hydrolysis of organic P fractions mediated by extracellular enzymes. The δ¹⁸O_P values of the NaOH extracts were above the calculated equilibrium value reflecting the balance state between microbial uptake of phosphate and the release of intracellular phosphate back to the soil. The HCl extracts with the lowest δ¹⁸O_P values and highest phosphate concentrations indicated that the HCl fraction was affected by microbial activity. Hence, these δ¹⁸O_p values likely reflected the oxygen isotopic values of the parent materials. The results suggested that phosphate oxygen isotope analyses could be an effective tool in order to trace phosphate sources, transformation processes, and its utilization by microorganisms in agricultural soils.     

Sediment pollution and dynamic in the Mar Piccolo of Taranto (southern Italy): insights from bottom sediment traps and surficial sediments

Major and trace element, PAH, and PCB concentrations were measured in surface sediments and particles from sediment traps collected in the First and Second Basin of the Mar Piccolo (Gulf of Taranto) in two periods (June–July and August–September, 2013). The aim of the study was to evaluate pollution degree, sediment transport and particle redistribution dynamic within the area. Results confirm the higher contamination of sediments from the First Basin observed by previous researches, particularly for Cu, Hg, Pb, total PAHs, and total PCBs. Advective transport from the First to the Second Basin appears to be the leading transfer mechanism of particles and adsorbed contaminants, as evidenced by measured fluxes and statistical analyses of contaminant concentrations in surficial sediments and particles from sediment traps. Long-range selective transports of PAHs and microbial anaerobic degradation processes for PCBs have been also observed. These results are limited to a restricted time window but are consistent with the presence of transport fluxes at the bottom of the water column. This mechanism deserves further investigation and monitoring activities, potentially being the main responsible of pollutant delivering to the less contaminated sectors of the Mar Piccolo.     

Alginate beads containing water treatment residuals for arsenic removal from water—formation and adsorption studies

Water treatment residuals (WTRs) produced in large quantities during deironing and demanganization of infiltration water, due to high content of iron and manganese oxides, exhibit excellent sorptive properties toward arsenate and arsenite. Nonetheless, since they consist of microparticles, their practical use as an adsorbent is limited by difficulties with separation from treated solutions. The aim of this study was entrapment of chemically pretreated WTR into calcium alginate polymer and examination of sorptive properties of the obtained composite sorbent toward As(III) and As(V). Different products were formed varying in WTR content as well as in density of alginate matrix. In order to determine the key parameters of the adsorption process, both equilibrium and kinetic studies were conducted. The best properties were exhibited by a sorbent containing 5 % residuals, formed in alginate solution with a concentration of 1 %. In slightly acidic conditions (pH 4.5), its maximum sorption capacity was 3.4 and 2.9 mg g^?1 for As(III) and As(V), respectively. At neutral pH, the adsorption effectiveness decreased to 3.3 mg As g^?1 for arsenites and to 0.7 mg As g^?1 for arsenates. The presence of carboxylic groups in polymer chains impeded in neutral conditions the diffusion of anions into sorbent beads; therefore, the main rate-limiting step of the adsorption, mainly in the case of arsenates, was intraparticle diffusion. The optimal condition for simultaneous removal of arsenates and arsenites from water by means of the obtained composite sorbent is slightly acidic pH, ensuring similar adsorption effectiveness for both arsenic species.     

Suitability of passive sampling for the monitoring of pharmaceuticals in Finnish surface waters

The occurrence of five pharmaceuticals, consisting of four anti-inflammatory and one antiepileptic drug, was studied by passive sampling and grab sampling in northern Lake Päijänne and River Vantaa. The passive sampling was performed by using Chemcatcher® sampler with a SDB-RPS Empore disk as a receiving phase. In Lake Päijänne, the sampling was conducted during summer 2013 at four locations near the discharge point of a wastewater treatment plant and in the years 2013 and 2015 at four locations along River Vantaa. The samples were analyzed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS) in the multiple reaction monitoring mode. The concentrations of carbamazepine, diclofenac, ibuprofen, ketoprofen, and naproxen in Lake Päijänne determined by passive sampling ranged between 1.4–2.9 ng L^?1, 15–35 ng L^?1, 13–31 ng L^?1, 16–27 ng L^?1, and 3.3–32 ng L^?1, respectively. Similarly, the results in River Vantaa ranged between 1.2–40 ng L^?1, 15–65 ng L^?1, 13–33 ng L^?1, 16–31 ng L^?1, and 3.3–6.4 ng L^?1. The results suggest that the Chemcatcher passive samplers are suitable for detecting pharmaceuticals in lake and river waters.     

Hydroponic root mats for wastewater treatment—a review

Hydroponic root mats (HRMs) are ecotechnological wastewater treatment systems where aquatic vegetation forms buoyant filters by their dense interwoven roots and rhizomes, sometimes supported by rafts or other floating materials. A preferential hydraulic flow is created in the water zone between the plant root mat and the bottom of the treatment system. When the mat touches the bottom of the water body, such systems can also function as HRM filter; i.e. the hydraulic flow passes directly through the root zone. HRMs have been used for the treatment of various types of polluted water, including domestic wastewater; agricultural effluents; and polluted river, lake, stormwater and groundwater and even acid mine drainage. This article provides an overview on the concept of applying floating HRM and non-floating HRM filters for wastewater treatment. Exemplary performance data are presented, and the advantages and disadvantages of this technology are discussed in comparison to those of ponds, free-floating plant and soil-based constructed wetlands. Finally, suggestions are provided on the preferred scope of application of HRMs.     

Economics of carbon dioxide capture and utilization—a supply and demand perspective

Lately, the technical research on carbon dioxide capture and utilization (CCU) has achieved important breakthroughs. While single CO₂-based innovations are entering the markets, the possible economic effects of a large-scale CO₂ utilization still remain unclear to policy makers and the public. Hence, this paper reviews the literature on CCU and provides insights on the motivations and potential of making use of recovered CO₂ emissions as a commodity in the industrial production of materials and fuels. By analyzing data on current global CO₂ supply from industrial sources, best practice benchmark capture costs and the demand potential of CO₂ utilization and storage scenarios with comparative statics, conclusions can be drawn on the role of different CO₂ sources. For near-term scenarios the demand for the commodity CO₂ can be covered from industrial processes, that emit CO₂ at a high purity and low benchmark capture cost of approximately 33 €/t. In the long-term, with synthetic fuel production and large-scale CO₂ utilization, CO₂ is likely to be available from a variety of processes at benchmark costs of approx. 65 €/t. Even if fossil-fired power generation is phased out, the CO₂ emissions of current industrial processes would suffice for ambitious CCU demand scenarios. At current economic conditions, the business case for CO₂ utilization is technology specific and depends on whether efficiency gains or substitution of volatile priced raw materials can be achieved. Overall, it is argued that CCU should be advanced complementary to mitigation technologies and can unfold its potential in creating local circular economy solutions.     

Potential of fly ash for neutralisation of acid mine drainage

Lignite (PK), bituminous (FI) and biomass (SE) fly ashes (FAs) were mineralogically and geochemically characterised, and their element leachability was studied with batch leaching tests. The potential for acid neutralisation (ANP) was quantified by their buffering capacity, reflecting their potential for neutralisation of acid mine drainage. Quartz was the common mineral in FAs detected by XRD with iron oxide, anhydrite, and magnesioferrite in PK, mullite and lime in FI, and calcite and anorthite in SE. All the FAs had high contents of major elements such as Fe, Si, Al and Ca. The Ca content in SE was six and eight times higher compared to PK and FI, respectively. Sulphur content in PK and SE was one magnitude higher than FI. Iron concentrations were higher in PK. The trace element concentrations varied between the FAs. SE had the highest ANP (corresponding to 275 kg CaCO₃?tonne^?1) which was 15 and 10 times higher than PK and FI, respectively. The concentrations of Ca²⁺, SO₄ ^2?, Na⁺ and Cl^? in the leachates were much higher compared to other elements from all FA samples. Iron, Cu and Hg were not detected in any of the FA leachates because of their mild to strong alkaline nature with pH ranging from 9 to 13. Potassium leached in much higher quantity from SE than from the other ashes. Arsenic, Mn and Ni leached from PK only, while Co and Pb from SE only. The concentrations of Zn were higher in the leachates from SE. The FAs used in this study have strong potential for the neutralisation of AMD due to their alkaline nature. However, on the other hand, FAs must be further investigated, with scaled-up experiments before full-scale application, because they might leach pronounced concentrations of elements of concern with decreasing pH while neutralising AMD.