Use of local waste for biochar production: Influence of feedstock and pyrolysis temperature on chromium removal from aqueous solutions.

Sediment enrichment with biochar, a high-carbon material produced by the pyrolysis of biomass, is a promising remediation strategy for metal pollution. The metal immobilization capacity of biochar can be explained by its porous structure, surface functional groups, pH greater than 7, and cation exchange capacity. However, the effectiveness in reducing metal bioavailability depends on the physicochemical characteristics of the biochar, which are strongly associated with the process conditions and feedstock. The aims of this study were to analyze the effect of pyrolysis temperature on the properties of biochars derived from different locally available biomass materials, biochar potential to adsorb Cr, and biochar phytotoxicity in seed germination. Poultry litter (PL), maize straw, the macrophyte Juncus imbricatus, and phytoremediation wastes from the macrophyte previously exposed to Cr were pyrolyzed into biochar at 300 °C and 600 °C. The properties and capacity of biochar to remove Cr from the aqueous phase were determined. Finally, a germination assay was performed to evaluate biochar phytotoxicity. Biochar yield decreased with increasing pyrolysis temperature, whereas ash content and pH increased. Biochar C content and total surface area increased with temperature. Biochar Cr removal capacity improved under the highest temperature, reaching a maximum sorption value of 13.7 mg g-1 Cr at 300 °C in PL biochar and of 42.6 mg g-1 Cr at 600 °C in J. imbricatus biochar. Despite the comparatively high metal content in the biochar, the germination indices of all biochars produced at 600 °C were higher than 80%, suggesting no phytotoxicity. Considering the metal sorption capacity and the phytotoxicity, biochars produced from J. imbricatus, PL, and phytoremediation residues at 600 °C were suitable for use in the removal of Cr from water. Integr Environ Assess Manag 2023;19:717-725. © 2022 SETAC.

Comparison Between Two Submerged Macrophytes as Biomonitors of Trace Elements Related to Anthropogenic Activities in the Ctalamochita River, Argentina.

The temporal variation of As, Co, Cr, Cu, Fe, Mn, Ni, Pb, V and Zn in surface waters and sediments, and trace element accumulation and physiological changes in the macrophytes Stuckenia filiformis and Potamogeton pusillus, were estimated in the Ctalamochita River, Argentina, both upstream and downstream of Río Tercero. Chromium, Fe, Pb and Zn in surface water were higher at the downstream site, while Cu and Mn were higher upstream. Chromium, Mn and Zn in S. filiformis correlated with concentrations observed in sediments, whereas only Zn did in water. In P. pusillus, As, Co, Cr, Ni, Pb and Zn correlated with concentrations in sediments. P. pusillus revealed greater variations in the photosynthetic pigments and malondialdehyde content in the site downstream of the city than those observed in S. filiformis. Therefore, P. pusillus has a greater potential use in monitoring studies in aquatic environments with ecological risk than S. filiformis.

Pb accumulation in spores of arbuscular mycorrhizal fungi.

Heavy metal (HM) pollution of soils is one of the most important and unsolved environmental problems affecting the world, with alternative solutions currently being investigated through different approaches. Arbuscular mycorrhizal fungi (AMF) are soil inhabitants that form symbiotic relationships with plants. This alleviates HM toxicity in the host plant, thereby enhancing tolerance. However, the few investigations that have addressed the presence of metals in the fungus structures were performed under experimental conditions, with there being no results reported for Pb. The current study represents a first approximation concerning the capability of spores to accumulate Pb in the AMF community present in a Pb polluted soil under field conditions. Micro X-ray fluorescence was utilized to obtain a direct observation of Pb in spores, and the innovation of total reflection X-ray fluorescence was applied to obtain Pb quantification in spores. The AMF community included species of Ambisporaceae, Archaeosporaceae, Gigasporacea, Glomeraceae and Paraglomeraceae, and was tolerant to high Pb concentrations in soil. Pb accumulation in AMF spores was demonstrated at the community level and corroborated by direct observation of the most abundant spores, which belonged to the Gigasporaceae group. Spore Pb accumulation is possibly dependent on the AMF and host plant species.

Accumulation of aluminium and physiological status of tree foliage in the vicinity of a large aluminium smelter.

A pollution gradient was observed in tree foliage sampled in the vicinity of a large aluminium production facility in Patagonia (Argentina). Leaves of Eucalyptus rostrata, and Populus hybridus and different needle ages of Pinus spec. were collected and concentrations of aluminium (Al) and sulphur (S) as well as physiological parameters (chlorophyll and lipid oxidation products) were analyzed. Al and S concentrations indicate a steep pollution gradient in the study showing a relationship with the physiological parameters in particular membrane lipid oxidation products. The present study confirms that aluminium smelting results in high Al and sulphur deposition in the study area, and therefore further studies should be carried out taking into account potentially adverse effects of these compounds on human and ecosystem health.

Effects of elevated CO2 concentrations and fly ash amended soils on trace element accumulation and translocation among roots, stems and seeds of Glycine max (L.) Merr.

The carbon dioxide (CO(2)) levels of the global atmosphere and the emissions of heavy metals have risen in recent decades, and these increases are expected to produce an impact on crops and thereby affect yield and food safety. In this study, the effects of elevated CO(2) and fly ash amended soils on trace element accumulation and translocation in the root, stem and seed compartments in soybean [Glycine max (L.) Merr.] were evaluated. Soybean plants grown in fly ash (FA) amended soil (0, 1, 10, 15, and 25% FA) at two CO(2) regimes (400 and 600 ppm) in controlled environmental chambers were analyzed at the maturity stage for their trace element contents. The concentrations of Br, Co, Cu, Fe, Mn, Ni, Pb and Zn in roots, stems and seeds in soybeans were investigated and their potential risk to the health of consumers was estimated. The results showed that high levels of CO(2) and lower concentrations of FA in soils were associated with an increase in biomass. For all the elements analyzed except Pb, their accumulation in soybean plants was higher at elevated CO(2) than at ambient concentrations. In most treatments, the highest concentrations of Br, Co, Cu, Fe, Mn, and Pb were found in the roots, with a strong combined effect of elevated CO(2) and 1% of FA amended soils on Pb accumulation (above maximum permitted levels) and translocation to seeds being observed. In relation to non-carcinogenic risks, target hazard quotients (TQHs) were significant in a Chinese individual for Mn, Fe and Pb. Also, the increased health risk due to the added effects of the trace elements studied was significant for Chinese consumers. According to these results, soybean plants grown for human consumption under future conditions of elevated CO(2) and FA amended soils may represent a toxicological hazard. Therefore, more research should be carried out with respect to food consumption (plants and animals) under these conditions and their consequences for human health.

Accumulation of polycyclic aromatic hydrocarbons and trace elements in the bioindicator plants Tillandsia capillaris and Lolium multiflorum exposed at PM10 monitoring stations in Stuttgart (Germany).

The accumulation of polycyclic aromatic hydrocarbons (PAHs) in Tillandsia capillaris Ruiz and Pav. form capillaris and trace elements in T. capillaris and Lolium multiflorum (LAM) cv. Lema was assessed and evaluated in the city of Stuttgart, Germany. Several sites (urban, suburban and rural) categorized according to type and intensity of vehicular traffic were investigated. At these sites, plants of T. capillaris and standardized cultures of L. multiflorum were exposed to ambient air. Foliar concentrations of PAHs (16 priority pollutants according to US-EPA) and of the trace elements Br, Co, Cu, Fe, Mn, Ni, Pb and Zn were determined. A high level of vehicular traffic was associated with the largest concentrations of PM(10) in ambient air and with the highest contents of PAHs and heavy metals in the bioindicator plants. The results showed a similar pattern between T. capillaris and the standardized biomonitor L. multiflorum. Therefore, these results allow us to propose T. capillaris as a suitable bioindicator to assess the distribution of pollution impacts caused by PAHs and trace elements in different subtropical and tropical regions.

Nickel exposure enhances the susceptibility of lichens Usnea amblyoclada and Ramalina celastri to urban atmospheric pollutants.

In the present study, the effect of nickel incorporation on the chemical response of Ramalina celastri (Spreng.) Krog & Swinsc. and Usnea amblyoclada (Müll. Arg.) Zahlbr. exposed to urban atmospheric pollutants was assessed. Lichen thalli were treated with Ni solutions and then transplanted to two areas of the city of Córdoba with different levels of pollution. After exposure, the concentration of chlorophyll a, chlorophyll b, phaeophytin a, hydroperoxy conjugated dienes, malondialdehyde, sulphur content, electric conductivity of the immersion water, and nickel content were measured. Also, a Pollution Index was calculated for each lichen species. The exposure to Ni altered the physiological response to atmospheric pollutants in both lichen species, making them more sensitive to any damage caused by them. When the species were compared, it was observed that R. celastri accumulated more sulphur than U. amblyoclada.

Applications of redundancy analysis for the detection of chemical response patterns to air pollution in lichen.

The lichens Ramalina celastri (Spreng.) Krog & Swinsc., Punctelia microsticta (Müll. Arg.) Krog and Canomaculina pilosa (Stizenb.) Elix & Hale were transplanted simultaneously to 17 urban-industrial sites in a northwestern area of Córdoba city, Argentina. The transplantation sites were set according to different environmental conditions: traffic, industries, tree cover, building height, topographic level, position in the block and distances from the river and from the power plant. Three months later, chlorophyll a, chlorophyll b, phaeophytin a, soluble proteins, hydroperoxy conjugated dienes, malondialdehyde concentration and sulfur accumulation were determined, and a pollution index was calculated for each sampling site. Redundancy analysis was applied to detect the variation pattern of the lichen variables that can be 'best' explained by the environmental variables considered. The present study provides information about both the specific pattern response of each species to atmospheric pollution, and environmental conditions that determine it. As regards pollutants emission sources R. celastri showed a chemical response associated mainly with pollutant released by the power plant and traffic. P. microsticta and C. pilosa responded mainly to industrial sources. Regarding environmental conditions that affect the spreading of air pollutants and their incidence on the bioindicator, the topographic level and tree cover surrounding the sampling site were found to be important for R. celastri, tree cover surrounding the sampling site and the building height affected P. microsticta, while building height did so for C. pilosa.

Air pollutants effect on monoterpenes composition and foliar chemical parameters in Schinus areira L.

Monoterpenes, pigments, lipid peroxidation products, sulfur and water content expressed as dry weight/fresh weight ratio were measured in leaves of Schinus areira L. collected in Mendoza, Argentina. The sampling sites showed different SO(2), NO(2) and PM(10) levels, which allowed setting out zones by mapping. Foliar chemical parameters in S. areira were analysed in relation to these zones. High hydroperoxy conjugated dienes (HPCD) and alpha-phellandrene content in foliar samples coming from areas with high SO(2) levels were measured. Principal component analysis (PCA) showed a positive association among SO(2), HPCD, malondialdehyde, sabinene and beta-pinene. In relation to NO(2) levels high values of chlorophyll (Chl)-b and Chl-b/Chl-a ratio were found. PCA showed for NO(2), an association with Chl-b/Chl-a, phaeophytin-a/Chl-a ratios and alpha-phellandrene. As regard PM(10), no significant differences were found in the chemical parameters indicating foliar damage, whereas the contents of tricyclene, alpha-pinene and beta-pinene showed low values in the area with high levels of this pollutant. From the results, it can be inferred that the more noticeable changes in the foliar chemistry of S. areira were detected in relation to the different SO(2) levels. This response was associated to an increase in the foliar oxidation processes accompanied by modifications in the levels of terpenes. This is important, as SO(2) was the only pollutant whose values in the annual arithmetic mean were over the standard value of 30 ppb.

Atmospheric quality and distribution of heavy metals in Argentina employing Tillandsia capillaris as a biomonitor.

The atmospheric quality and distribution of heavy metals were evaluated throughout a wide region of Argentina. In addition, the biomonitor performance of Tillandsia capillaris Ruiz & Pav. f. capillaris was studied in relation to the accumulation of heavy metals and to its physiologic response to air pollutants. A sampling area of 50,000 km2 was selected in the central region of the Argentine Republic. This area was subdivided into grids of 25 x 25 km. Pools of T. capillaris, where present, were collected at each intersection point. From each pool three sub-samples were analyzed independently. Furthermore, five replicates were collected at 20% of the points in order to analyze the variability within the site. The content of Co, Cu, Fe, Ni, Mn, Pb and Zn was determined by Atomic Absorption Spectrometry. Chemical-physiological parameters were also determined to detect symptoms of foliar damage. Chlorophylls, phaeophytins, hydroperoxy conjugated dienes, malondialdehyde and sulfur were quantified in T. capillaris. Some of these parameters were used to calculate a foliar damage index. Data sets were evaluated by one-way ANOVA, correlation analysis, principal component analysis and mapping. Geographical distribution patterns were obtained for the different metals reflecting the contribution of natural and anthropogenic emission sources. According to our results it can be inferred that Fe, Mn and Co probably originated in the soil. For Pb, the highest values were found in the mountainous area, which can be attributed to the presence of Pb in the granitic rocks. Ni showed mainly an anthropogenic origin, with higher values found in places next to industrial centers. For Zn the highest values were in areas of agricultural development. The same was observed for Cu, whose presence could be related to the employment of pesticides. The foliar damage index distribution map showed that the central and southeastern zones were the ones where the major damage in the bioindicator was found. The central zone coincides with the city of Córdoba whereas the southeastern area is strictly agricultural, so the high values found there could be related to the use of pesticides.

Comparison among air pollutants, meteorological conditions and some chemical parameters in the transplanted lichen Usnea amblyoclada.

The response of Usnea amblyoclada (Müll. Arg.) Zahlbr. to real concentrations of atmospheric pollutants measured by two automatic monitoring stations, was studied in Córdoba City, Argentina. The influence of different weather conditions on the biomonitor's response was also assessed. The concentration of chlorophyll a, chlorophyll b, hydroperoxy-conjugated dienes, and malondialdehyde were quantified in lichen thalli collected from a clean area and in transplanted thalli after 1 month of exposure in an urban area, from April to October, 1996. The dry weight/fresh weight, chlorophyll b/chlorophyll a and phaeophytin a/chlorophyll a ratios were also calculated. Data sets were evaluated by two-way analysis of variance and correlation analysis. It was observed that hydroperoxy-conjugated dienes, malondialdehyde, chlorophylls, and pigment degradation increase during winter-time, when higher levels of suspended particles, non-methane hydrocarbons, hydrogen sulfide and ozone were also measured. These findings would be connected mainly with meteorological conditions, as most pollutants did not exceed prescribed threshold levels.

Chemical response of transplanted lichen Canomaculina pilosa to different emission sources of air pollutants.

The lichen Canomaculina pilosa was transplanted to 21 sampling sites, plus two controls sites in a north-western area of Córdoba City, Argentina. The transplantation sites were set according to traffic levels, industry condition and distances from the power plant. On the transplanted lichens chlorophyll a, chlorophyll b, phaeophytin a, soluble proteins, hydroperoxy-conjugated dienes, malondialdehyde concentration and sulphur accumulation were determined. A pollution index was calculated for each sampling site. The present study provides information about chemical parameters showing variations as the response of C. pilosa to different emission sources of air pollutants. The C. pilosa chemical response was mainly associated to industries. Significant higher values were observed in phaeophytin a/chlorophyll a ratio, sulphur content and pollution index values in lichen material transplanted at sites with industry. For the distance from the power plant category, only the hydroperoxy-conjugated dienes concentration showed significant differences. For the different traffic levels no significant variations were observed for any of the chemical parameters quantified.

Relationship between foliar chemical parameters measured in Melia azedarach L. and environmental conditions in urban areas.

A diagnostic study was done on Melia azedarach L. in relation to atmospheric pollutants in Córdoba city, Argentina. The study area receives regional pollutants, and it was categorized taking into account traffic level, industrial level, location of the sample point in relation to the corner, treeless condition, building type, topographic level and distance to the river. Water content and Specific Leaf Area (SLA) were calculated; and concentrations of soluble proteins, sulphur, hydroperoxy conjugated dienes (HPCD), chlorophylls (Total Chl) and pheophytins (Total Paeoph) were determined in leaf samples. HPCD correlated positively with industry, topographic level and distance to the river, and with a combination of the environmental variables (ECI); pigments correlated negatively with traffic level and with ECI; Total Phaeoph/Total Chl ratio correlated positively with traffic, building and ECI. On the basis of our results, traffic level, industrial level, building type, topographic level and distance to the river are the environmental variables to bear in mind when selecting analogous sampling points in a passive monitoring program. An approximation to predict tree injury may be obtained by measuring water content, soluble proteins, sulphur, HPCD and pigments as they are responsible for the major variability of data. This study revealed that M. azedarach was sensitive to air pollutants from traffic and industry. Thus, in those sampling sites with the maximum score for traffic level, industrial level and ECI, the highest values of the parameters that indicate foliar damage together with the least pigment concentration were observed.

Chemical response of the lichen Punctelia subrudecta (Nyl.) Krog transplanted close to a power station in an urban-industrial environment.

The lichen Punctelia subrudecta (Nyl.) Krog was transplanted to 22 biomonitoring sites in a northwestern area of Córdoba city, Argentina and tested for chlorophyll a, chlorophyll b, phaeophytin a, soluble protein, hydroperoxy conjugated dienes (HPCD), malondialdehyde (MDA) concentration and sulphur accumulation. A pollution index (PI) was calculated for each biomonitoring site. The biomonitoring sites were set according to (1) traffic levels, (2) industrial density and (3) distance of the power station close to each site. The biomonitor's chemical response was associated with industries as well as power stations. Significant differences were observed in sulphur content, MDA concentration and PI values in lichen material transplanted to sites with different industrial densities. The higher values for these parameters were found at sites with high industrial levels. At the same time, significant differences were detected for sulphur content in samples at different distances from the power station, with higher accumulation in samples located far from the power plant. For MDA concentration, effect of different levels of industrial density was observed only at points close to the power station, probably because of higher levels of humidity near the power plant. For PI significantly higher values were observed in samples at points far from the power station and with high industrial density. This shows the additive effect of the principal emission sources that act on the response of P. subrudecta to air pollutants.

Differences in responses to urban air pollutants by Ligustrum lucidum Ait. and Ligustrum lucidum Ait. f. tricolor (Rehd.) Rehd.

This study examined the chemical response of Ligustrum lucidum Ait. and Ligustrum lucidum Ait. f. tricolor (Rehd.) Rehd. when exposed to different sources of atmospheric pollutants. Dry weight/fresh weight ratio, specific leaf area (SLA), sulfur content, chlorophyll concentration, carotenoids, soluble proteins, malondialdehyde (MDA) and hydroperoxy conjugated dienes (HPCD) were determined for leaf samples taken from different sites in the city of Córdoba, Argentina. These sites were categorized in terms of their traffic levels and industrial levels. Both L. lucidum as well as L. lucidum f. tricolor accumulated sulfur in their leaves in sites with high traffic levels, the former being the most sensitive to this type of pollution. Ligustrum lucidum exhibited significantly low concentrations of soluble proteins, in sites with high industrial pollution levels. Ligustrum lucidum f. tricolor did not exhibit a significant response to industrial pollution.

Biomonitoring of air pollutants from traffic and industries employing Ramalina ecklonii (Spreng.) Mey. and Flot. in Córdoba, Argentina.

The lichen Ramalina ecklonii (Spreng.) Mey. and Flot. was transplanted to 29 biomonitoring sites in the southeastern area of Córdoba, Argentina and tested for chlorophyll a, phaeophytin a, conjugated dienes concentration, malondialdehyde, soluble protein content and sulfur accumulation. The biomonitoring sites were determined according to (i) vehicular traffic levels, and (ii) industrial density, i.e. number and type of industries (small and medium) close to each of the sites. Each of the two groups were then broken down into three categories which provided a basis for performance analysis and quantification of the chemical parameters in the biomonitor. A pollution index (P.I.) was calculated based on the ratio of phaeophytin a to chlorophyll a and ratio of sulfur, malonaldehyde and conjugated dienes in transplanted specimens to sulfur, malonaldehyde and conjugated dienes in the freshly picked specimens. Significant differences were observed in sulfur content and P.I. in lichen samples that had been transplanted to sites with different vehicular traffic levels. At the same time, significant differences in the phaeophytin a concentration, phaeophytin a/chlorophyll a ratio and P.I. were observed at sites characterized by different levels of industrial density (all with low-to-medium traffic).