Increased bioavailability of metals in two contrasting agricultural soils treated with waste wood-derived biochar and ash

Recycled waste wood is being increasingly used for energy production; however, organic and metal contaminants in by-products produced from the combustion/pyrolysis residue may pose a significant environmental risk if they are disposed of to land. Here we conducted a study to evaluate if highly polluted biochar (from pyrolysis) and ash (from incineration) derived from Cu-based preservative-treated wood led to different metal (e.g., Cu, As, Ni, Cd, Pb, and Zn) bioavailability and accumulation in sunflower (Helianthus annuus L.). In a pot experiment, biochar at a common rate of 2 % w/w, corresponding to ～50 t ha^?1, and an equivalent pre-combustion dose of wood ash (0.2 % w/w) were added to a Eutric Cambisol (pH 6.02) and a Haplic Podzol (pH 4.95), respectively. Both amendments initially raised soil pH, although this effect was relatively short-term, with pH returning close to the unamended control within about 7 weeks. The addition of both amendments resulted in an exceedance of soil Cu statutory limit, together with a significant increase of Cu and plant nutrient (e.g., K) bioavailability. The metal-sorbing capacity of the biochar, and the temporary increase in soil pH caused by adding the ash and biochar were insufficient to offset the amount of free metal released into solution. Sunflower plants were negatively affected by the addition of metal-treated wood-derived biochar and led to elevated concentration of metals in plant tissue, and reduced above- and below-ground biomass, while sunflower did not grow at all in the Haplic Podzol. Biochar and ash derived from wood treated with Cu-based preservatives can lead to extremely high Cu concentrations in soil and negatively affect plant growth. Identifying sources of contaminated wood in waste stream feedstocks is crucial before large-scale application of biochar or wood ash to soil is considered.     

Nutrient and enzymatic changes of hydrolysed tannery solid waste treated with epigeic earthworm Eudrilus eugeniae and phytotoxicity assessment on selected commercial crops

Animal fleshing (ANFL) is the predominant proteinaceous solid waste generated during processing of leather and it is confronting disposal problems. The aim of this study was to assess the potential of epigeic earthworm Eudrilus eugeniae to utilize and transform the fermented ANFL in the solid state (SSF) and submerged state (SmF) into a value added product along a low residence period (25 days). A total of six treatment units containing different waste mixture compositions were established. Fifty healthy and non-clitellated earthworms were introduced in three different treatment containers: control, SSF, and SmF (+worm). Another set of treatment mixtures (control, SSF, SmF) was established without earthworms (?worm) to compare the results. The products were characterized for physico-chemical, enzymatic analysis and seedling growth parameters to compare the differences in the process with and without earthworms. The changes observed in the analytical parameters were in the following order: SSF > SmF > control mixtures (p?<?0.05). The vermicompost showed a significant reduction in heavy metals, total organic carbon and an increase in total Kjeldhal nitrogen as compared to the product untreated by earthworms. The maximum enzymatic activities were observed after 21 days of vermicomposting. The relative seed germination of vermicompost extracts were in the order of tomato (Lycopersicon esculentum) > green gram (Vigna radiata) > cucumber (Cucumis sativus) > bottle gourd (Lagenaria siceraria (Mol.) Standl.) and showed no phytotoxicity effects. The results indicated that the combination of both ANFL hydrolysis through fermentation and vermicomposting is a good alternative to the management of this kind of waste.     

Green synthesis of silver nanoparticles by microorganism using organic pollutant: its antimicrobial and catalytic application

A novel approach for the green synthesis of silver nanoparticles (AgNPs) from aqueous solution of AgNO₃ using culture supernatant of phenol degraded broth is reported in this work. The synthesis was observed within 10 h, and AgNPs showed characteristic surface plasmon resonance around 410 nm. Spherical nanoparticles of size less than 30 nm were observed in transmission electron microscopy. X-ray diffraction pattern corresponding to 111, 200, 220, and 311 revealed the crystalline nature of the as-formed nanoparticles. It was found that the colloidal solution of AgNP suspensions exhibited excellent stability over a wide range of ionic strength, pH, and temperature. The effect of pH and ionic strength indicated that stabilization is due to electrostatic repulsion arising from the negative charge of the conjugate proteins. The AgNPs showed highly potent antimicrobial activity against Gram-positive, Gram-negative, and fungal microorganisms. The as-prepared AgNPs showed excellent catalytic activity in reduction of 4-nitrophenol to 4-aminophenol by NaBH₄. By manufacturing magnetic alginate beads, the reusability of the AgNPs for the catalytic reaction has been demonstrated.     

Photocatalytic degradation of acetaminophen in modified TiO2 under visible irradiation

This study investigated the photocatalytic degradation of acetaminophen (ACT) in synthetic titanium dioxide (TiO₂) solution under a visible light (λ >440 nm). The TiO₂ photocatalyst used in this study was synthesized via sol–gel method and doped with potassium aluminum sulfate (KAl(SO₄)₂) and sodium aluminate (NaAlO₂). The influence of some parameters on the degradation of acetaminophen was examined, such as initial pH, photocatalyst dosage, and initial ACT concentration. The optimal operational conditions were also determined. Results showed that synthetic TiO₂ catalysts presented mainly as anatase phase and no rutile phase was observed. The results of photocatalytic degradation showed that LED alone degraded negligible amount of ACT but with the presence of TiO₂/KAl(SO₄)₂, 95 % removal of 0.10-mM acetaminophen in 540-min irradiation time was achieved. The synthetic TiO₂/KAl(SO₄)₂ presented better photocatalytic degradation of acetaminophen than commercially available Degussa P-25. The weak crystallinity of synthesized TiO₂/NaAlO₂ photocatalyst showed low photocatalytic degradation than TiO₂/KAl(SO₄)₂. The optimal operational conditions were obtained in pH 6.9 with a dose of 1.0 g/L TiO₂/KAl(SO₄)₂ at 30 °C. Kinetic study illustrated that photocatalytic degradation of acetaminophen fits well in the pseudo-first order model. Competitive reactions from intermediates affected the degradation rate of ACT, and were more obvious as the initial ACT concentration increased.     

Marine organisms as heavy metal bioindicators in the Persian Gulf and the Gulf of Oman

In the present study, cadmium and lead concentrations were compared in barnacles, ghost shrimps, polychaetes, bivalves, and sediment from ten different locations along the intertidal zone of the Persian Gulf and the Gulf of Oman. The results revealed significant differences in the heavy metal concentrations between the organisms with barnacles showing, by far, the highest metal concentrations. The bioaccumulation factor of Cd in different animals follows this pattern with barnacles?>?bivalves?>?polychaetes?>?ghost shrimps, while the pattern for Pb was barnacles?>?polychaetes?>?bivalves?>?ghost shrimps. In most of the stations, sediments showed the lowest lead and cadmium concentrations. Therefore, it is concluded that barnacles with Pb concentrations between 0.17 and 2,016.1 μg/g and Cd concentrations ranging from 0.4 to 147.1 μg/g are the best organisms to be employed in monitoring programs designed to assess pollution with bioavailable metals in the Persian Gulf and the Gulf of Oman.     

Biomass smoke in Burkina Faso: what is the relationship between particulate matter,carbon monoxide,and kitchen characteristics?

In Burkina Faso where cooking with biomass is very common, little information exists regarding kitchen characteristics and their impact on air pollutant levels. The measurement of air pollutants such as respirable particulate matter (PM₁₀), an important component of biomass smoke that has been linked to adverse health outcomes, can also pose challenges in terms of cost and the type of equipment needed. Carbon monoxide could potentially be a more economical and simpler measure of air pollution. The focus of this study was to first assess the association of kitchen characteristics with measured PM₁₀ and CO levels and second, the relationship of PM₁₀ with CO concentrations, across these different kitchen characteristics in households in Nouna, Burkina Faso. Twenty-four-hour concentrations of PM₁₀ (area) were measured with portable monitors and CO (area and personal) estimated using color dosimeter tubes. Data on kitchen characteristics were collected through surveys. Most households used both wood and charcoal burned in three-stone and charcoal stoves. Mean outdoor kitchen PM₁₀ levels were relatively high (774 μg/m³, 95 % CI 329–1,218 μg/m³), but lower than indoor concentrations (Satterthwaite t value, ?6.14; p?<?0.0001). In multivariable analyses, outdoor kitchens were negatively associated with PM₁₀ (OR?=?0.06, 95 % CI 0.02–0.16, p value <0.0001) and CO (OR?=?0.03, 95 % CI 0.01–0.11, p value <0.0001) concentrations. Strong area PM₁₀ and area CO correlations were found with indoor kitchens (Spearman’s r?=?0.82, p?<?0.0001), indoor stove use (Spearman’s r?=?0.82, p?<?0.0001), and the presence of a smoker in the household (Spearman’s r?=?0.83, p?<?0.0001). Weak correlations between area PM₁₀ and personal CO levels were observed with three-stone (Spearman’s r?=?0.23, p?=?0.008) and improved stoves (Spearman’s r?=?0.34, p?=?0.003). This indicates that the extensive use of biomass fuels and multiple stove types for cooking still produce relatively high levels of exposure, even outdoors, suggesting that both fuel subsidies and stove improvement programs are likely necessary to address this problem. These findings also indicate that area CO color dosimeter tubes could be a useful measure of area PM₁₀ concentrations when levels are influenced by strong emission sources or when used in indoors. The weaker correlation observed between area PM₁₀ and personal CO levels suggests that area exposures are not as useful as proxies for personal exposures, which can vary widely from those recorded by stationary monitors.     

Formation of indoor nitrous acid (HONO) by light-induced NO<Subscript>2</Subscript> heterogeneous reactions with white wall paint

Gaseous nitrogen dioxide (NO₂) represents an oxidant that is present in relatively high concentrations in various indoor settings. Remarkably increased NO₂ levels up to 1.5 ppm are associated with homes using gas stoves. The heterogeneous reactions of NO₂ with adsorbed water on surfaces lead to the generation of nitrous acid (HONO). Here, we present a HONO source induced by heterogeneous reactions of NO₂ with selected indoor paint surfaces in the presence of light (300 nm?<?λ?<?400 nm). We demonstrate that the formation of HONO is much more pronounced at elevated relative humidity. In the presence of light (5.5 W m^?2), an increase of HONO production rate of up to 8.6?·?10⁹ molecules cm^?2 s^?1 was observed at [NO₂]?=?60 ppb and 50 % relative humidity (RH). At higher light intensity of 10.6 (W m^?2), the HONO production rate increased to 2.1?·?10¹⁰ molecules cm^?2 s^?1. A high NO₂ to HONO conversion yield of up to 84 % was observed. This result strongly suggests that a light-driven process of indoor HONO production is operational. This work highlights the potential of paint surfaces to generate HONO within indoor environments by light-induced NO₂ heterogeneous reactions.     

Evaluation of different isotherm models,kinetic, thermodynamic,and copper biosorption efficiency of Lobaria pulmonaria (L.) Hoffm.

The biosorption characteristics of Cu(II) ions from aqueous solution using Lobaria pulmonaria (L.) Hoffm. biomass were investigated. The biosorption efficiency of Cu(II) onto biomass was significantly influenced by the operating parameters. The maximum biosorption efficiency of L. pulmonaria was 65.3% at 10 mg/L initial metal concentration for 5 g/L lichen biomass dosage. The biosorption of Cu(II) ions onto biomass fits the Langmuir isotherm model and the pseudo-second-order kinetic model well. The thermodynamic parameters indicate the feasibility and exothermic and spontaneous nature of the biosorption. The effective desorption achieved with HCl was 96%. Information on the nature of possible interactions between the functional groups of the L. pulmonaria biomass and Cu(II) ions was obtained via Fourier transform infrared (FTIR) spectroscopy. The results indicated that the carboxyl (–COOH) and hydroxyl (–OH) groups of the biomass were mainly involved in the biosorption of Cu(II) onto L. pulmonaria biomass. The L. pulmonaria is a promising biosorbent for Cu(II) ions because of its availability, low cost, and high metal biosorption and desorption capacities.

Implications: Lobaria pulmonaria is a promising biosorbent for Cu(II) ions because of its availability, low cost, and high metal biosorption and desorption capacities. To the best of our knowledge, this is the first paper on the biosorption Cu by L. pulmonaria.     

Emission,speciation, and evaluation of impacts of non-methane volatile organic compounds from open dump site

Surface emission from Dhapa, the only garbage disposal ground in Kolkata, is a matter of concern to the local environment and also fuels the issues of occupational and environmental health. Surface emission of the Dhapa landfill site was studied using a flux chamber measurement for nonmethane volatile organic compounds (NMVOCs). Eighteen noncarbonyl volatile organic compounds (VOCs) and 14 carbonyl VOCs, including suspected and known carcinogens, were found in appreciable concentrations. The concentrations of the target species in the flux chamber were found to be significantly higher for most of the species in summer than winter. Surface emission rate of landfill gas was estimated by using two different approaches to assess the applicability for an open landfill site. It was found that the emissions predicted using the model Land GEM version 3.02 is one to two orders less than the emission rate calculated from flux chamber measurement for the target species. Tropospheric ozone formation has a serious impact for NMVOC emission. The total ozone-forming potential (OFP) of the Dhapa dumping ground considering all target NMVOCs was estimated to be 4.9E+04 and 1.2E+05 g/day in winter and summer, respectively. Also, it was found that carbonyl VOCs play a more important role than noncarbonyl VOCs for tropospheric ozone formation. Cumulative cancer risk estimated for all the carcinogenic species was found to be 2792 for 1 million population, while the total noncancer hazard index (HI) was estimated to be 246 for the occupational exposure to different compounds from surface emission to the dump-site workers at Dhapa.

Implications:This paper describes the real-time surface emission of NMVOCs from an open municipal solid waste (MSW) dump site studied using a flux chamber. Our study findings indicate that while planning for new landfill site in tropical meteorology, real-time emission data must be considered, rather than relying on modeled data. The formation of tropospheric ozone from emitted NMVOC has also been studied. Our result shows how an open landfill site acts as a source and adds to the tropospheric ozone for the airshed of a metropolitan city.     

PM10 concentration levels at an urban and background site in Cyprus: The impact of urban sources and dust storms

Air quality in Cyprus is influenced by both local and transported pollution, including desert dust storms. We examined PM₁₀ concentration data collected in Nicosia (urban representative) from April 1, 1993, through December 11, 2008, and in Ayia Marina (rural background representative) from January 1, 1999, through December 31, 2008. Measurements were conducted using a Tapered Element Oscillating Micro-balance (TEOM). PM₁₀ concentrations, meteorological records, and satellite data were used to identify dust storm days. We investigated long-term trends using a Generalized Additive Model (GAM) after controlling for day of week, month, temperature, wind speed, and relative humidity. In Nicosia, annual PM₁₀ concentrations ranged from 50.4 to 63.8 μg/m³ and exceeded the EU annual standard limit enacted in 2005 of 40 μg/m³ every year. A large, statistically significant impact of urban sources (defined as the difference between urban and background levels) was seen in Nicosia over the period 2000–2008, and was highest during traffic hours, weekdays, cold months, and low wind conditions. Our estimate of the mean (standard error) contribution of urban sources to the daily ambient PM₁₀ was 24.0 (0.4) μg/m³. The study of yearly trends showed that PM₁₀ levels in Nicosia decreased from 59.4 μg/m³ in 1993 to 49.0 μg/m³ in 2008, probably in part as a result of traffic emission control policies in Cyprus. In Ayia Marina, annual concentrations ranged from 27.3 to 35.6 μg/m³, and no obvious time trends were observed. The levels measured at the Cyprus background site are comparable to background concentrations reported in other Eastern Mediterranean countries. Average daily PM₁₀ concentrations during desert dust storms were around 100 μg/m³ since 2000 and much higher in earlier years. Despite the large impact of dust storms and their increasing frequency over time, dust storms were responsible for a small fraction of the exceedances of the daily PM₁₀ limit.

ImplicationsThis paper examines PM₁₀ concentrations in Nicosia, Cyprus, from 1993 to 2008. The decrease in PM₁₀ levels in Nicosia suggests that the implementation of traffic emission control policies in Cyprus has been effective. However, particle levels still exceeded the European Union annual standard, and dust storms were responsible for a small fraction of the daily PM₁₀ limit exceedances. Other natural particles that are not assessed in this study, such as resuspended soil and sea salt, may be responsible in part for the high particle levels.