Properties of biochars from conventional and alternative feedstocks and their suitability for metal immobilization in industrial soil

In contaminated soils, excessive concentrations of metals and their high mobility pose a serious environmental risk. A suitable soil amendment can minimize the negative effect of metals in soil. This study investigated the effect of different biochars on metal (Cu, Pb, Zn) immobilization in industrial soil. Biochars produced at 300 and 600 °C from conventional (MS, maize silage; WP, wooden pellets) and alternative (SC, sewage sludge compost; DR, digestate residue) feedstocks were used as soil amendments at a dosage of 10 % (w/w). The type of feedstock and pyrolysis temperature affected the properties of the biochars and their ability to immobilize metal in soil. Compared to production at 300 °C, all biochars produced at 600 °C had higher pH (6.2–10.7), content of ash (7.2–69.0 %) and fixed carbon (21.1–56.7 %), but lower content of volatile matter (9.7–37.2 %). All biochars except DR biochar had lower dissolved organic carbon (DOC) content (1.4–2.3 g C/L) when made at 600 °C. Only MS and SC biochars had higher cation exchange capacity (25.2 and 44.7 cmol/kg, respectively) after charring at 600 °C. All biochars contained low concentrations of Cd, Cu, Ni, Pb and Zn; Cd was volatilized to the greatest extent during pyrolysis. Based on FTIR analysis and molar ratios of H/C and O/C, biochars had a greater degree of carbonization and aromaticity after charring at 600 °C. The efficiency of the biochars in metal immobilization depended mainly on their pH, ash content, and concentration of DOC. SC and DR biochars were more effective for Cu and Zn immobilization than MS and WP biochars, which makes them attractive options for large-scale soil amendment.     

Potential risk assessment of heavy metals by consuming shellfish collected from Xiamen, China

Concentrations of Hg, Pb, Cd, and Cr in 240 shellfish including oyster, short-necked clam, razor clam, and mud clam collected from six administrative regions in Xiamen of China were measured. The daily intakes of heavy metals through the consumption of shellfish were estimated based on both of the metal concentrations in shellfish and the consuming amounts of shellfish. In addition, the target hazard quotients (THQ) were used to evaluate the potential risk of heavy metals in shellfish on human body. Results showed that the concentrations of heavy metals in shellfish ranged at the following sequence: Cr > Cd > Pb > Hg. The concentrations of Hg and Pb in most samples were below the limits (0.3 mg?kg^?1 for Hg and 0.5 mg?kg^?1 for Pb) of national standard (GB 18406.4-2001) set in China. About 57 % of samples were found to contain more than 0.1 mg?kg^?1 of Cd, in which the highest level was found in oyster from Xiangan with a value of 1.21 mg?kg^?1. The average concentrations of Cd in oyster and mud clam samples were 0.338 and 0.369 mg?kg^?1, respectively, which were significantly higher (p?<?0.05) than those in the samples of short-necked clam and razor clam. The highest concentration of Cr was found to present in short-necked clam from Jimei with a value of 10.4 mg?kg^?1, but a mean value of 1.95 mg?kg^?1 in all the shellfish was observed, and no significant difference was found among the different sampling regions. The calculated daily intakes of Hg, Pb, Cd, and Cr through consuming the shellfish were 0.005, 0.122, 0.137, and 1.20 μg?kg^?1 day^?1, respectively, which accounted for 2.19, 3.42, 13.7, and 40.1 % of the corresponding tolerable limits suggested by the Joint FAO/WHO Expert Committee on Food Additives. The THQ values of the four metals were far below 1 for most samples, except for those of Cd and Cr in the four shellfish species with the mean values of 0.132 and 0.385, respectively. The highest THQ values of Cd were observed in the species of oyster (0.719) and mud clam (0.568). But the high THQ values of Cr observed in all the four species were derived from the applied reference dose (RfD) data of Cr(VI) due to the unavailable RfD value of total Cr. The results indicate that the intakes of heavy metals by consuming shellfish collected from Xiamen of China do not present an appreciable hazard risk on human health, but attention should be paid to consuming those with relatively high THQ values, such as oyster, mud clam, and short-necked clam.     

Heavy metal accumulation by poplar in calcareous soil with various degrees of multi-metal contamination: implications for phytoextraction and phytostabilization

The object of this study was to assess the capacity of Populus alba L. var. pyramidalis Bunge for phytoremediation of heavy metals on calcareous soils contaminated with multiple metals. In a pot culture experiment, a multi-metal-contaminated calcareous soil was mixed at different ratios with an uncontaminated, but otherwise similar soil, to establish a gradient of soil metal contamination levels. In a field experiment, poplars with different stand ages (3, 5, and 7 years) were sampled randomly in a wastewater-irrigated field. The concentrations of cadmium (Cd), Cu, lead (Pb), and zinc (Zn) in the poplar tissues and soil were determined. The accumulation of Cd and Zn was greatest in the leaves of P. pyramidalis, while Cu and Pb mainly accumulated in the roots. In the pot experiment, the highest tissue concentrations of Cd (40.76 mg kg^?1), Cu (8.21 mg kg^?1), Pb (41.62 mg kg^?1), and Zn (696 mg kg^?1) were all noted in the multi-metal-contaminated soil. Although extremely high levels of Cd and Zn accumulated in the leaves, phytoextraction using P. pyramidalis may take at least 24 and 16 years for Cd and Zn, respectively. The foliar concentrations of Cu and Pb were always within the normal ranges and were never higher than 8 and 5 mg kg^?1, respectively. The field experiment also revealed that the concentrations of all four metals in the bark were significantly higher than that in the wood. In addition, the tissue metal concentrations, together with the NH₄NO₃-extractable concentrations of metals in the root zone, decreased as the stand age increased. P. pyramidalis is suitable for phytostabilization of calcareous soils contaminated with multiple metals, but collection of the litter fall would be necessary due to the relatively high foliar concentrations of Cd and Zn.     

Australian native plant species Carpobrotus rossii (Haw.) Schwantes shows the potential of cadmium phytoremediation

Many polluted sites are typically characterized by contamination with multiple heavy metals, drought, salinity, and nutrient deficiencies. Here, an Australian native succulent halophytic plant species, Carpobrotus rossii (Haw.) Schwantes (Aizoaceae) was investigated to assess its tolerance and phytoextraction potential of Cd, Zn, and the combination of Cd and Zn, when plants were grown in soils spiked with various concentrations of Cd (20–320 mg kg^?1 Cd), Zn (150–2,400 mg kg^?1 Zn) or Cd + Zn (20?+?150, 40?+?300, 80?+?600 mg kg^?1). The concentration of Cd in plant parts followed the order of roots > stems > leaves, resulting in Cd translocation factor (TF, concentration ratio of shoots to roots) less than one. In contrast, the concentration of Zn was in order of leaves > stems > roots, with a Zn TF greater than one. However, the amount of Cd and Zn were distributed more in leaves than in stems or roots, which was attributed to higher biomass of leaves than stems or roots. The critical value that causes 10 % shoot biomass reduction was 115 μg g^?1 for Cd and 1,300 μg g^?1 for Zn. The shoot Cd uptake per plant increased with increasing Cd addition while shoot Zn uptake peaked at 600 mg kg^?1 Zn addition. The combined addition of Cd and Zn reduced biomass production more than Cd or Zn alone and significantly increased Cd concentration, but did not affect Zn concentration in plant parts. The results suggest that C. rossii is able to hyperaccumulate Cd and can be a promising candidate for phytoextraction of Cd from polluted soils.     

Accumulation of Cr,Cd, Pb,Cu, and Zn by plants in tanning sludge storage sites: opportunities for contamination bioindication and phytoremediation

Tanning sludge enriched with high concentrations of Cr and other metals has adverse effects on the environment. Plants growing in the metalliferous soils may have the ability to cope with high metal concentrations. This study focuses on potentials of using native plants for bioindication and/or phytoremediation of Cr-contaminated sites. In the study, we characterized plants and soils from six tanning sludge storage sites. Soil in these sites exhibited toxic levels of Cr (averaged 16,492 mg kg^?1) and other metals (e.g., 48.3 mg Cu kg^?1, 2370 mg Zn kg^?1, 44.9 mg Pb kg^?1, and 0.59 mg Cd kg^?1). Different metal tolerance and accumulation patterns were observed among the sampled plant species. Phragmites australis, Zephyranthes candida, Cynodon dactylon, and Alternanthera philoxeroides accumulated moderate-high concentrations of Cr and other metals, which could make them good bioindicators of heavy metal pollution. High Cr and other metal concentrations (e.g., Cd and Pb) were found in Chenopodium rubrum (372 mg Cr kg^?1), Aster subulatus (310 mg Cr kg^?1), and Brassica chinensis (300 mg Cr kg^?1), being considered as metal accumulators. In addition, Nerium indicum and Z. candida were able to tolerate high concentrations of Cr and other metals, and they may be used as preferable pioneer species to grow or use for restoration in Cr-contaminated sites. This study can be useful for establishing guidelines to select the most suitable plant species to revegetate and remediate metals in tanning sludge-contaminated fields.     

Effect of biochars on adsorption of Cu(II), Pb(II) and Cd(II) by three variable charge soils from southern China

The purpose of this study is to compare the relative contribution of different mechanisms to the enhanced adsorption of Cu(II), Pb(II) and Cd(II) by variable charge soils due to incorporation of biochars derived from crop straws. The biochars were prepared from the straws of canola and peanut using an oxygen-limited pyrolysis method at 350 °C. The effect of biochars on adsorption and desorption of Cu(II), Pb(II) and Cd(II) by and from three variable charge soils from southern China was investigated with batch experiments. Based on the desorption of pre-adsorbed heavy metals, the electrostatic and non-electrostatic adsorptions were separated. EDTA was used to replace the heavy metals complexed with biochars and to evaluate the complexing ability of the biochars with the metals. The incorporation of biochars increased the adsorption of Cu(II), Pb(II) and Cd(II) by the soil; peanut straw char induced a greater increase in the adsorption of the three metals. The increased percentage of Cd(II) adsorption induced by biochars was much greater than that for the adsorption of Cu(II) and Pb(II). Cu(II) adsorption on three variable charge soils was enhanced by the two biochars mainly through a non-electrostatic mechanism, while both electrostatic and non-electrostatic mechanisms contributed to the enhanced adsorption of Pb(II) and Cd(II) due to the biochars. Peanut straw char had a greater specific adsorption capacity than canola straw char and thus induced more non-electrostatic adsorption of Cu(II), Pb(II) and Cd(II) by the soils than did the canola straw char. The complexing ability of the biochars with Cu(II) and Pb(II) was much stronger than that with Cd(II) and thus induced more specific adsorption of Cu(II) and Pb(II) by the soils than that of Cd(II). Biochars increased heavy metal adsorption by the variable charge soils through electrostatic and non-electrostatic mechanisms, and the relative contribution of the two mechanisms varied with metals and biochars.     

Characterization of Cd-, Pb-, Zn-resistant endophytic Lasiodiplodia sp. MXSF31 from metal accumulating Portulaca oleracea and its potential in promoting the growth of rape in metal-contaminated soils

The aim of this study was to characterize the features of a Cd-, Pb-, and Zn-resistant endophytic fungus Lasiodiplodia sp. MXSF31 and to investigate the potential of MXSF31 to remove metals from contaminated water and soils. The endophytic fungus was isolated from the stem of Portulaca oleracea growing in metal-contaminated soils. The maximum biosorption capacities of MXSF31 were 3.0?×?10³, 1.1?×?10⁴, and 1.3?×?10⁴ mg kg^?1 for Cd, Pb, and Zn, respectively. The biosorption processes of Cd, Pb, and Zn by MXSF31 were well characterized with the pseudo-second-order kinetic model. The biosorption isotherm processes of Pb and Zn by the fungus were fitted better with the Langmuir model, while the biosorption processes of Cd was better fitted with the Freundlich model. The biosorption process of MXSF31 was attributed to the functional groups of hydroxyl, amino, carbonyl, and benzene ring on the cell wall. The active biomass of the strain removed more Cd, Pb, and Zn (4.6?×?10⁴, 5.6?×?10⁵, and 7.0?×?10⁴ mg kg^?1, respectively) than the dead biomass. The inoculation of MXSF31 increased the biomass of rape (Brassica napus L.), the translocation factor of Cd, and the extraction amount of Cd by rape in the Cd?+?Pb-contaminated soils. The results indicated that the endophytic fungus strain had the potential to remove heavy metals from water and soils contaminated by multiple heavy metals, and plants accumulating multiple metals might harbor diverse fungi suitable for bioremediation of contaminated media.     

Effects of alkaline and bioorganic amendments on cadmium,lead, zinc,and nutrient accumulation in brown rice and grain yield in acidic paddy fields contaminated with a mixture of heavy metals

Paddy soils and rice (Oryza sativa L.) contaminated by mixed heavy metals have given rise to great concern. Field experiments were conducted over two cultivation seasons to study the effects of steel slag (SS), fly ash (FA), limestone (LS), bioorganic fertilizer (BF), and the combination of SS and BF (SSBF) on rice grain yield, Cd, Pb, and Zn and nutrient accumulation in brown rice, bioavailability of Cd, Pb, and Zn in soil as well as soil properties (pH and catalase), at two acidic paddy fields contaminated with mixed heavy metals (Cd, Pb, and Zn). Compared to the controls, SS, LS, and SSBF at both low and high additions significantly elevated soil pH over both cultivation seasons. The high treatments of SS and SSBF markedly increased grain yields, the accumulation of P and Ca in brown rice and soil catalase activities in the first cultivation season. The most striking result was from SS application (4.0 t ha^?1) that consistently and significantly reduced the soil bioavailability of Cd, Pb, and Zn by 38.5–91.2 % and the concentrations of Cd and Pb in brown rice by 20.9–50.9 % in the two soils over both cultivation seasons. LS addition (4.0 t ha^?1) also markedly reduced the bioavailable Cd, Pb, and Zn in soil and the Cd concentrations in brown rice. BF remobilized soil Cd and Pb leading to more accumulation of these metals in brown rice. The results showed that steel slag was most effective in the remediation of acidic paddy soils contaminated with mixed heavy metals.     

Monitoring of non-destructive sampling strategies to assess the exposure of avian species in Jiangsu Province,China to heavy metals

To assess the exposure of avian species in Jiangsu Province, China to eight heavy metals (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn), the flight feathers, eggshells and feces of total ten avian species (including four herons, four cranes, one stork and one gull) were collected during March to May in 2012. The total concentrations of As, Cd and Hg were measured by Atomic Fluorescence Spectrometer; Cr, Cu, Ni, Pb and Zn were measured by inductively coupled plasma optical emission spectrometer. The determined concentrations of Cr (3.94, 1.33–8.30 mg kg^?1), Cu (15.02, 7.34–35.53 mg kg^?1) and Zn (134.66, 77.26–242.25 mg kg^?1) in fresh feathers and Cd (7.93, 7.44–9.12 mg kg^?1), Ni (22.74, 19.38–24.71 mg kg^?1), Pb (85.06, 78.72–91.95 mg kg^?1) and Zn (63.54, 55.82–72.14 mg kg^?1) in eggshells were higher than the mean values of other reported data, indicating a considerable heavy metal pollution status in local area. Comparing to the heavy metal levels in early historic feathers (1992–2000), a significant elevation of concentrations has been observed in recent bird feathers. For feathers of Grus japonensis, the heavy metal concentrations increased by 19–267%. This increased tendency was consistent with local GDP (Gross Domestic Products) development. The anthropogenic economic activity especially industrial development may be a critical reason that caused the increase of heavy metal levels in local avian species.     

Occurrence,spatial distribution,sources, and risks of polychlorinated biphenyls and heavy metals in surface sediments from a large eutrophic Chinese lake (Lake Chaohu)

Surface sediment from large and eutrophic Lake Chaohu was investigated to determine the occurrence, spatial distribution, sources, and risks of polychlorinated biphenyls (PCBs) and heavy metals in one of the five biggest freshwater lakes in China. Total concentration of PCBs (Σ₃₄PCBs) in Lake Chaohu was 672 pg g^?1 dry weight (dw), with a range of 7 to 3999 pg g^?1 dw, which was lower than other water bodies worldwide. The majority of heavy metals were detected at all sampling locations, except for Sr, B, and In. Concentrations of Al, Fe, Ca, Mn, Sr, Co, Zn, Cd, Pb, and Hg were similar to that reported for other lakes globally. Concentrations of K, Mg, Na, Li, Ga, and Ag were greater than the average, whereas those of Cr, Ni, and Cu were lower. Cluster analysis (CA) and positive matrix factorization (PMF) yielded accordant results for the source apportionment of PCBs. The technical PCBs and microbial degradation accounted for 34.2 % and 65.8 % of total PCBs using PMF, and PMF revealed that natural and anthropogenic sources of heavy metals accounted for 38.1 % and 61.8 %, respectively. CA indicated that some toxic heavy metals (e.g., Cd, In, Tl, and Hg) were associated with Ca–Na–Mg minerals rather than Fe–Mn minerals. The uncorrelated results between organic matter revealed by pyrolysis technology and heavy metals might be caused by the existence of competitive adsorption between organic matter and minerals. PCBs and heavy metals were coupling discharge without organochlorine pesticides (OCPs), but with polycyclic aromatic hydrocarbons (PAHs) and polybrominated diphenyl ethers (PBDEs). No sediment sample exceeded the toxic threshold for dioxin-like PCBs (dl-PCBs) set at 20 pg toxicity equivalency quantity (TEQ)?g^?1, (max dl-PCBs, 10.9 pg TEQ g^?1). However, concentrations of Ag, Cd, and Hg were at levels of environmental concern. The sediment in the drinking water source area (DWSA) was threatened by heavy metals from other areas, and some fundamental solutions were proposed to protect the DWSA.     

Evaluation of toxic metal (Hg, Cd, Pb), polychlorinated biphenyl (PCBs), and pesticide (DDTs) levels in aromatic herbs collected in selected areas of Southern Italy

This study provides, for the first time, data regarding levels of toxic metals (Hg, Cd, and Pb) and organochlorine compounds (PCBs and DDTs) in various aromatic herbs as rosemary (Rosmarinus officinalis), sage (Salvia officinalis), laurel (Laurus nobilis), oregano (Origanum vulgare), and spearmint (Mentha viridis) collected in some towns of the Southern Italy with different anthropogenic and population pressure. Metal and organochlorine compound concentrations were determined using atomic absorption spectrophotometer and gas-chromatography mass spectrometer (GC/MS), respectively. Pb emerged as the most abundant element, followed by Cd and Hg, while between organochlorine compounds, PCB concentrations were higher than those of DDTs. The pollutant concentrations were found to vary depending on the different herbs. The highest Pb levels were observed in rosemary (1.66 μg g^?1 dry weight) and sage (1.41 μg g^?1 dry weight), this latter showing also the highest Cd concentrations (0.75 μg g^?1 dry weight). For PCBs, the major concentrations were found in rosemary (2.75 ng g^?1 dry weight) and oregano (2.39 ng g^?1 dry weight). The principal component analysis applied in order to evaluate possible similarities and/or differences in the contamination levels among sampling sites indicated differences area-specific contamination.     

Phytoscreening and phytoextraction of heavy metals at Danish polluted sites using willow and poplar trees

The main purpose of this study was to determine typical concentrations of heavy metals (HM) in wood from willows and poplars, in order to test the feasibility of phytoscreening and phytoextraction of HM. Samples were taken from one strongly, one moderately, and one slightly polluted site and from three reference sites. Wood from both tree species had similar background concentrations at 0.5 mg kg^?1 for cadmium (Cd), 1.6 mg kg^?1 for copper (Cu), 0.3 mg kg^?1 for nickel (Ni), and 25 mg kg^?1 for zinc (Zn). Concentrations of chromium (Cr) and lead (Pb) were below or close to detection limit. Concentrations in wood from the highly polluted site were significantly elevated, compared to references, in particular for willow. The conclusion from these results is that tree coring could be used successfully to identify strongly heavy metal-polluted soil for Cd, Cu, Ni, Zn, and that willow trees were superior to poplars, except when screening for Ni. Phytoextraction of HMs was quantified from measured concentration in wood at the most polluted site. Extraction efficiencies were best for willows and Cd, but below 0.5 % over 10 years, and below 1?‰ in 10 years for all other HMs.     

Assessing the enrichment of heavy metals in surface soil and plant (Digitaria eriantha) around coal-fired power plants in South Africa

Nine metals (Fe, Cu, Mn, Ni, Cd, Pb, Hg, Cr, and Zn) were determined in soil and Digitaria eriantha plants within the vicinity of three coal power plants (Matla, Lethabo, and Rooiwal), using ICP-OES and GFAAS. The total metal concentration in soil ranged from 0.05?±?0.02 to 1836?±?70 μg g^?1, 0.08?±?0.05 to 1744?±?29 μg g^?1, and 0.07?±?0.04 to 1735?±?91 μg g^?1 in Matla, Lethabo, and Rooiwal, respectively. Total metal concentration in the plant (D. eriantha) ranged from 0.005?±?0.003 to 535?±?43 μg g^?1 in Matla, 0.002?±?0.001 to 400?±?269 μg g^?1 in Lethabo, and 0.002?±?0.001 to 4277?±?201 μg g^?1 in Rooiwal. Accumulation factors (A) of less than 1 (i.e., 0.003 to 0.37) at all power plants indicate a low transfer of metal from soil to plant (excluder). Enrichment factor values obtained (2.4–5.0) indicate that the soils are moderately enriched with the exception of Pb that had significant enrichment of 20. Geo-accumulation index (I-geo) values of metals indicate that the soils are moderately polluted (0.005–0.65), except for Pb that showed moderate to strong pollution (1.74–2.53).     

Mineral constituents in Leccinum scabrum from lowland locations in the central Europe and their relation to concentration in forest topsoil

Leccinum scabrum is an edible mushroom common in European regions in the northern hemisphere. Macro and trace mineral constituents such as Ag, Al, Ba, Ca, Cd, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, P, Rb, Sr and Zn were studied in L. scabrum and in the top soil collected from the same location underneath soil substratum. The “pseudo-total” and labile (extractable fraction of minerals) were measured to get insight into the levels, distribution between the morphological parts of fruiting bodies, potential for their bioconcentration by mushroom and evaluated for human exposure via consumption of the mushroom. The sampling sites include the Dar?lubska Wilderness, Trójmiejski Landscape Park, Sobieszewo Island, Wdzydze Landscape Park and outskirts of the K?trzyn town in Mazury from the norther part of Poland. Median values of K, Rb and P concentrations in dehydrated L. scabrum were for caps in range 27,000–44,000 mg kg^?1, 90–320 mg kg^?1 and 6,200–9,100 mg kg^?1, and followed by Mg at 880–1,000 mg kg^?1, Ca at 48–210 mg kg^?1 and Al at 15–120 mg kg^?1. The median concentrations of Cu, Fe, Mn and Zn in caps were in range 15–27 mg kg^?1 db 38–140 mg kg^?1, 5.3–27 mg kg^?1 and 130–270 mg kg^?1. For Ba and Sr, concentrations on the average were at ～1 mg kg^?1, and almost equally distributed between the caps and stipes of the fruiting bodies. L. scabrum mushrooms were low in toxic Ag, Cd, Hg and Pb, for which the median values in dried caps from five locations were, respectively, in range 0.48–0.98 mg kg^?1 (cap to stipe index, Q_C/S, was 2.5–4.1), 1.0–5.8 mg kg^?1 (Q_C/S 2.9–3.8), 0.36–0.59 mg kg^?1 (Q_C/S 1.6–2.7) and 0.20–0.91 mg kg^?1 (Q_C/S 1.2–1.9). Substantial variations in the concentrations of the “pseudo-total” fraction (extracted by aqua regia) or labile fraction (extracted by 20% solution of nitric acid) of the elements determined in forest topsoils were noted between some of the locations examined. The elements K, P, Cd, Cu, Hg, Mn, Na, Rb and Zn can be considered as those which were bioconcentrated by L. scabrum in fruiting bodies, while the rates of accumulation varied with the sampling location.     

Polycyclic aromatic hydrocarbons and trace metals in mosque’s carpet dust of Riyadh,Saudi Arabia,and their health risk implications

The main objectives of this work were to identify and determine the concentrations of polycyclic aromatic hydrocarbons (PAHs) and trace metals in carpet dust samples from various mosques of the city of Riyadh and to assess the health risks associated with the exposure to these pollutants. Therefore, 31 samples of mosque’s carpet dust from Riyadh were collected. The results showed that 14 PAHs were present in the dust samples with concentrations ranged from 90 to 22,146 ng g^?1 (mean = 4096 ± 4277 ng g^?1) where low molecular weight compounds were dominant. The presence of PAHs were in the order of naphthalene > chrysene and benzo(b)fluoranthene > benzo(a)pyrene > acenaphthene and benzo(k)fluoranthene > pyrene and the absence of indeno(1,2,3-cd)pyrene and dibenz(a,h)anthracene. The diagnostic ratio coupled with principle component analysis (PCA) revealed mix sources of petrogenic from traffic, stack emission, and pyrogenic inputs from essence and perfumed wood burning. Trace metals were significant in the dust samples, and their concentrations decrease in the order of Zn, Mn, Cu, Cr, Pb, Ni, and V where Zn being the highest (94.4 ± 91.5 μg g^?1) and indium was the lowest (1.9 ± 9.3 μg g^?1). The trace metals were major in southern and central parts of Riyadh and followed the order of central Riyadh > southern Riyadh > western Riyadh > eastern Riyadh > northern Riyadh. Estimated risk based on the total PAHs was found to be 4.30 × 10^?11 for adult and 1.56 × 10^?11 for children. Elemental non-cancer risk for adults ranged from 7.9 × 10^?4 for Co to 7.58 × 10^?1 for Li and for children ranged from 3.70 × 10^?3 for Co to 3.54 for Li. Policy implication and mitigations of PAHs in Riyadh and Saudi Arabia were highlighted.     

Removal of Cu, Zn, and Cd from aqueous solutions by the dairy manure-derived biochar

Purpose

Biochar derived from waste biomass is now gaining much attention for its function as a biosorbent for environmental remediation. The objective of this study was to determine the effectiveness of biochar as a sorbent in removing Cd, Cu, and Zn from aqueous solutions.

Methods

Biochar was produced from dairy manure (DM) at two temperatures: 200°C and 350°C, referred to as DM200 and DM350, respectively. The obtained biochars were then equilibrated with 0–5 mM Cu, Zn or Cd in 0.01 M NaNO₃ solution for 10 h. The changes in solution metal concentrations after sorption were evaluated for sorption capacity using isotherm modeling and chemical speciation Visual MINTEQ modeling, while the solid was collected for species characterization using infrared spectroscopy and X-ray elemental dot mapping techniques.

Results

The isotherms of Cu, Zn, and Cd sorption by DM200 were better fitted to Langmuir model, whereas Freundlich model well described the sorption of the three metals by DM350. The DM350 were more effective in sorbing all three metals than DM200 with both biochars had the highest affinity for Cu, followed by Zn and Cd. The maximum sorption capacities of Cu, Zn, and Cd by DM200 were 48.4, 31.6, and 31.9 mg g^?1, respectively, and those of Cu, Zn, and Cd by DM350 were 54.4, 32.8, and 51.4 mg g^?1, respectively. Sorption of the metals by the biochar was mainly attributed to their precipitation with PO ₄ ^3? or CO ₃ ^2? originating in biochar, with less to the surface complexation through –OH groups or delocalized π electrons. At the initial metal concentration of 5 mM, 80–100 % of Cu, Zn, and Cd retention by DM200 resulted from the precipitation, with less than 20 % from surface adsorption through phenonic –OH complexation. Among the precipitation, 20–30 % of the precipitation occurred as metal phosphate and 70–80 % as metal carbonate. For DM350, 75–100 % of Cu, Zn, and Cd retention were due to the precipitation, with less than 25 % to surface adsorption through complexation of heavy metal by phenonic –OH site or delocalized π electrons. Among the precipitation, only less than 10 % of the precipitation was present as metal phosphate and more than 90 % as metal carbonate.

Conclusions

Results indicated that dairy manure waste can be converted into value-added biochar as a sorbent for sorption of heavy metals, and the mineral components originated in the biochar play an important role in the biochar's high sorption capacity.     

Hazardous substances in indoor dust emitted from waste TV recycling facility

Various hazardous substances contained in waste TV sets might be released into environment via dust during recycling activities. Two brominated flame retardants (BFRs), polybrominated diphenyl ethers (PBDEs), and tetrabromobisphenol A (TBBPA), and five kinds of heavy metals (Cu, Pb, Cd, Cr, and Ni) were detected in indoor dust collected from two workshops (TV dismantling workshop and subsequent recycling workshop). PBDEs concentrations in dust from waste wires recycling line (722,000 ng/g) were the highest among the studied sites, followed by those in manual dismantling–sorting line (117,000 ng/g), whereas TBBPA concentrations were the highest in manual dismantling–sorting line (557 ng/g) and printed circuit board (PCB) recycling line (428 ng/g). For heavy metals, Cu and Pb were the most enriched metals in all dust samples. The highest concentration of Pb (22,900 mg/kg) was found in TV dismantling workshop-floor dust. Meanwhile, Cu was the predominant metal in dust from the PCB recycling line, especially in dust collected from electrostatic separation area (42,700 mg/kg). Occupational exposure assessment results showed that workers were the most exposed to BDE-209 among the four PBDE congeners (BDE-47, BDE-99, BDE-153, and BDE-209) in both workshops. The hazard quotient (HQ) indicated that noncancerous effects were unlikely for both BFRs and heavy metals (HQ?<?1), and carcinogenic risks for Cd, Cr, and Ni (risk?<?10^?6) on workers in two workshops were relatively low.     

Bio- and toxic elements in mushrooms from the city of Umeå and outskirts,Sweden

Edible mushrooms (Albatrellus ovinus, Boletus edulis, Clitocybe odora, Gomphidius glutinosus, Leccinum scabrum, Leccinum versipelle, Lycoperdon perlatum, Suillus bovinus, Suillus luteus, and Xerocomus subtomentosus) collected from unpolluted areas of the city of Umeå and its outskirts in the northern part of Sweden were examined for contents of toxic metallic elements (Cd, Pb, and Ag) and essential macro- and microelements (K, Na, Ca, Mg, Cu, Fe, Mn, and Zn) using a validated method and a final measurement by flame atomic absorption spectroscopy (F-AAS). The median values of the toxic metallic element concentrations (in mg kg^?1 dry biomass, db) ranged from: 0.12–3.9, 0.46–5.1, and 0.91–6.2 for Ag, Cd and Pb, respectively. For the essential metallic elements, the median values of concentrations ranged from: 24000–58000, 15–2000, 59–610, 520–1900, 2.0–97, 16–150, 15–120, and 4.3–26 mg kg^?1 db for K, Na, Ca, Mg, Cu, Zn, Fe, and Mn, respectively. The baseline concentrations of the metallic elements determined in mushrooms were mainly affected by the fungal species. The assessed probable maximal dietary intake of Cd (0.002 mg kg^?1 body mass) solely from a mushroom meal was only slightly below a revised value of the tolerable weekly intake for this element, while for Pb (0.003 mg kg^?1 body mass) it was tenfold below the provisionally tolerable weekly intake.     

Biochar- and phosphate-induced immobilization of heavy metals in contaminated soil and water: implication on simultaneous remediation of contaminated soil and groundwater

Long-term wastewater irrigation or solid waste disposal has resulted in the heavy metal contamination in both soil and groundwater. It is often separately implemented for remediation of contaminated soil or groundwater at a specific site. The main objective of this study was to demonstrate the hypothesis of simultaneous remediation of both heavy metal contaminated soil and groundwater by integrating the chemical immobilization and pump-and-treat methods. To accomplish the objective, three experiments were conducted, i.e., an incubation experiment was first conducted to determine how dairy-manure-derived biochar and phosphate rock tailing induced immobilization of Cd in the Cd-contaminated soils; second, a batch sorption experiment was carried out to determine whether the pre-amended contaminated soil still had the ability to retain Pb, Zn and Cd from aqueous solution. BCR sequential extraction as well as XRD and SEM analysis were conducted to explore the possible retention mechanism; and last, a laboratory-scale model test was undertaken by leaching the Pb, Zn, and Cd contaminated groundwater through the pre-amended contaminated soils to demonstrate how the heavy metals in both contaminated soil and groundwater were simultaneously retained and immobilized. The incubation experiment showed that the phosphate biochar were effective in immobilizing soil Cd with Cd concentration in TCLP (toxicity characteristics leaching procedure) extract reduced by 19.6 % and 13.7 %, respectively. The batch sorption experiment revealed that the pre-amended soil still had ability to retain Pb, Zn, and Cd from aqueous solution. The phosphate-induced metal retention was mainly due to the metal–phosphate precipitation, while both sorption and precipitation were responsible for the metal stabilization in the biochar amendment. The laboratory-scale test demonstrated that the soil amended with phosphate removed groundwater Pb, Zn, and Cd by 96.4 %, 44.6 %, and 49.2 %, respectively, and the soil amended with biochar removed groundwater Pb, Zn, and Cd by 97.4 %, 53.4 %, and 54.5 %, respectively. Meanwhile, the metals from both groundwater and soil itself were immobilized with the amendments, with the leachability of the three metals in the CaCl₂ and TCLP extracts being reduced by up to 98.1 % and 62.7 %, respectively. Our results indicate that the integrated chemical immobilization and pump-and-treat method developed in this study provides a novel way for simultaneous remediation of both metal-contaminated soil and groundwater.     

Concentration and dissipation of chlorantraniliprole and thiamethoxam residues in maize straw,maize, and soil

To study the dissipation rates and final residual levels of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil, two independent field trials were conducted during the 2014 cropping season in Beijing and Anhui Provinces of China. A 40% wettable powder (20% chlorantraniliprole?+?20% thiamethoxam) was sprayed onto maize straw and soil at an application rate of 118 g of active ingredient per hectare (g a.i.ha^?1). The residual concentrations were determined by ultra-high-performance liquid chromatography–tandem mass spectrometry. The chlorantraniliprole half-lives in maize straw and soil were 9.0–10.8 and 9.5–21.7 days, respectively. The thiamethoxam half-lives in maize straw and soil were 8.4–9.8 and 4.3–11.7 days, respectively. The final residues of chlorantraniliprole and thiamethoxam in maize straw, maize, and soil were measured after the pesticides had been sprayed two and three times with an interval of 7 days using 1 and 1.5 times the recommended rate (72 g a.i. ha^?1 and 108 g a.i. ha^?1, respectively). Representative maize straw, maize, and soil samples were collected after the last treatment at pre-harvest intervals of 7, 14, and 28 days. The chlorantraniliprole residue was below 0.01 mg kg^?1 in maize, between 0.01 and 0.31 mg kg^?1 in maize straw, and between 0.03 and 1.91 mg kg^?1 in soil. The thiamethoxam residue concentrations in maize, maize straw, and soil were <0.01, <0.01, and 0.01–0.03 mg kg^?1, respectively. The final pesticide residues on maize were lower than the maximum residue limit (MRL) of 0.02 mg kg^?1 after a 14-day pre-harvest interval. Therefore, a dosage of 72 g a.i. ha^?1 was recommended, as it can be considered safe to human beings and animals.