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.

Since the publication of the first version of European standard EN-1948 in 1996, long-term sampling equipment has been improved to a high standard for the sampling and analysis of polychlorodibenzo-p-dioxin (PCDD)/polychlorodibenzofuran (PCDF) emissions from industrial sources. The current automated PCDD/PCDF sampling systems enable to extend the measurement time from 6-8 h to 15-30 days in order to have data values better representative of the real pollutant emission of the plant in the long period. EN-1948:2006 is still the European technical reference standard for the determination of PCDD/PCDF from stationary source emissions. In this paper, a methodology to estimate the measurement uncertainty of long-term automated sampling is presented. The methodology has been tested on a set of high concentration sampling data resulting from a specific experience; it is proposed with the intent that it is to be applied on further similar studies and generalized. A comparison between short-term sampling data resulting from manual and automated parallel measurements has been considered also in order to verify the feasibility and usefulness of automated systems and to establish correlations between results of the two methods to use a manual method for calibration of automatic long-term one. The uncertainty components of the manual method are analyzed, following the requirements of EN-1948-3:2006, allowing to have a preliminary evaluation of the corresponding uncertainty components of the automated system. Then, a comparison between experimental data coming from parallel sampling campaigns carried out in short- and long-term sampling periods is realized. Long-term sampling is more reliable to monitor PCDD/PCDF emissions than occasional short-term sampling. Automated sampling systems can assure very useful emission data both in short and long sampling periods. Despite this, due to the different application of the long-term sampling systems, the automated results could not be directly compared with manual results, not even in terms of measurement uncertainty. This investigation focuses on both uncertainty and repeatability of the automated sampling method. The standard 20988, developed by Internarional Organization of Standardization (ISO) can be used to estimate the measurement uncertainty. The results confirm that the uncertainties of manual and automated methods are comparable. At the same time, it is not appropriate to consider the manual method as a reference for the evaluation of the uncertainty of the automated sampling system, due to the high variability of both systems.

Water is fundamental to the existence of life since it is essential to a series of activities, such as agriculture, power generation, and public and industrial supplies. The residual water generated by these activities is released into the environment, reaches the water systems, and becomes a potential risk to nontarget organisms. This paper reports the development and validation of a quantitative method, based on solid-phase extraction and liquid chromatography tandem mass spectrometry, for the simultaneous analysis of 18 pharmaceuticals and personal care products (PPCPs) and 33 pesticides in surface and drinking waters. The accuracy of the method was determined by calculating the recoveries, which ranged from 70 to 120 % for most pesticides and PPCPs, whereas limits of quantification ranged from 0.8 to 40 ng/L. After the validation step, the method was applied to drinking and surface waters. Pesticides and PPCPs were found in concentrations lower than 135.5 ng/L. The evaluation of different water sources with regard to contamination by pesticides and PPCPs has been quite poor in southern Brazil.

A flat plate serpentine reactor modified from ultraviolet disinfection pool in municipal wastewater treatment plants was developed for the removal of 17-ethinylestradiol (EE2) for the first time. The photocatalytic degradation performance of EE2 was investigated in this serpentine reactor under different conditions such as inlet concentrations, loaded catalyst concentrations, incident radiations fluxes, and flow velocities. More than 98 % of EE2 was removed under certain conditions within 120 min. An integrated model including a six-flux adsorption–scattering model and a modified flow diffusion model was established to investigate the effect of radiation field and flow velocities, respectively. A satisfactory agreement was observed between the model simulation and experimental results, showing a potential for design and scale-up of photocatalytic reactor for wastewater treatment.

Dynamics of livestock and poultry manure nutrient was analyzed at a provincial scale from 2002 to 2008. The nutrient capacity of 18 kinds of croplands and grasslands to assimilate nutrients was assessed in the same temporal–spatial scale. Manure nitrogen (N) had increased from 5.111 to 6.228 million tons (MT), while manure phosphorus (P) increased from 1.382 to 1.607 MT. Manure N and P share similar spatial patterns of yields, but proportion of specialized livestock husbandry and contribution of leading livestock categories (swine, cattle, cow, sheep, layer chicken, broiler chicken) were different. The nutrients generated from dominant seven provinces took more than about half of total manure N in China. After subtracting the chemical fertilizers, there were some manure nutrient capacities in western part of China. Risk analysis of manure nutrient pollution overload in eastern and southern parts of China was serious, which should restrict livestock's developments. Amount of chemical fertilizers applied should be reduced to make room for manure nutrients. For the sake of greenhouse effects, the emission of methane (CH₄) and nitrous oxide (NO ₓ ) emissions in China is serious for the global change, thus merits further statistics and studies. The spatial and temporal pattern of Chinese manure nutrient pollution from livestock and the assimilation capacity of cropland and grassland can provide useful information for policy development on Chinese soil environment and livestock.

Volatile organic compounds (VOCs) and particles emitted by incense sticks and candles combustion in an experimental room have been monitored on-line and continuously with a high time resolution using a state-of-the-art high sensitivity-proton transfer reaction-mass spectrometer (HS-PTR-MS) and a condensation particle counter (CPC), respectively. The VOC concentration–time profiles, i.e., an increase up to a maximum concentration immediately after the burning period followed by a decrease which returns to the initial concentration levels, were strongly influenced by the ventilation and surface interactions. The obtained kinetic data set allows establishing a qualitative correlation between the elimination rate constants of VOCs and their physicochemical properties such as vapor pressure and molecular weight. The emission of particles increased dramatically during the combustion, up to 9.1(±0.2) × 10⁴ and 22.0(±0.2) × 10⁴ part cm⁻³ for incenses and candles, respectively. The performed kinetic measurements highlight the temporal evolution of the exposure level and reveal the importance of ventilation and deposition to remove the particles in a few hours in indoor environments.

Phosphogypsum (PG) is a by-product of the phosphorus–fertiliser industry and represents an environmental concern since it contains pollutants such as cadmium (Cd). We have recently shown that the overexpression of a proton pump gene (TaVP1) in transgenic tobacco (Nicotiana tabacum) led to an enhanced Cd tolerance and accumulation. The aim of this study was to evaluate the potential of transgenic Arabidopsis thaliana plants harbouring the TaVP1 gene to phytoremediate phosphogypsum. A pot experiment was carried out under greenhouse conditions. Transgenic A. thaliana plants harbouring the TaVP1 gene were grown on various substrates containing phosphogypsum (0, 25, 50 and 100 %) for 40 days. At the end of the growth period, we examined the growth (germination, root length, fresh weight) and physiological parameters (chlorophyll and protein contents, catalase activity and proteolysis) as well as the cadmium, Mg, Ca, and P contents of the A. thaliana plants. In order to evaluate Cd tolerance of the A. thaliana lines harbouring the TaVP1 gene, an in vitro experiment was also carried out. One week-old seedlings were transferred to Murashige and Skoog agar plates containing various concentrations of cadmium; the germination, total leaf area and root length were determined. The growth and physiological parameters of all A. thaliana plants were significantly altered by PG. The germination capacity, root growth and biomass production of wild-type (WT) plants were more severely inhibited by PG compared with the TaVP1 transgenic A. thaliana lines. In addition, TaVP1 transgenic A. thaliana plants maintained a higher antioxidant capacity than the WT. Interestingly, elemental analysis of leaf material derived from plants grown on PG revealed that the transgenic A. thaliana line accumulated up to ten times more Cd than WT. Despite its higher Cd content, the transgenic A. thaliana line performed better than the WT counterpart. In vitro evaluation of Cd tolerance showed that TaVP1 transgenic A. thaliana lines were more Cd-tolerant than the WT plants. These results suggested that ectopic expression of a vacuolar proton pump in A. thaliana plants can lead to various biotechnological applications including the phytoremediation of industrial wastes.

The main objectives of this study were to (a) study the interaction between N and P cycles in mining-affected aquatic systems and (b) to quantify release rates of sedimentary soluble reactive phosphorus (SRP) that may be related to this interaction. Sediment cores and water from Lake Bruträsket (Boliden, northern Sweden) were collected and a time series of water sampling and flow measurements was conducted in the Brubäcken stream connected to the lake. Factors affecting SRP release were studied in a sediment incubation experiment and water column experiments. Field and laboratory measurements indicated that pH and dissolved oxygen are two important factors for SRP release. At the end of the low-oxygen incubation, an SRP concentration of 56 μg L(-1) resulted in a sedimentary flux of 1.1 mg SRP m(-2) day(-1). This is ∼10 times higher than the flux of 0.12 mg SRP m(-2) day(-1) obtained from depth integration of vertical SRP profiles measured in the lake, and ∼100 times higher than the external flux of 0.014 mg SRP m(-2) d(-1) into the lake (based on catchment area). Field measurements indicated that oxidation of organic matter and mining-related chemicals (ammonium and thiosulphates) may result in increased internal SRP flux from the sediment. Increased P loading in the lake as a result of low-oxygen conditions could change water column total nitrogen/total phosphorus ratios from 27 to 17, consequently changing the lake from being P-limited to be co-limited by N and P. The obtained findings point to possible interaction between the cycles of nitrogen (oxygen consumption) and P (flux from sediment) that may be important for nutrient regulation in mine water recipients.

Different batches of valued mussel shell and waste mussel shell ash are characterised. Shell ash has pH > 12 and high electrical conductivities (between 16.01 and 27.27 dS m⁻¹), while calcined shell shows pH values up to 10.7 and electrical conductivities between 1.19 and 3.55 dS m⁻¹. X-ray fluorescence, nitric acid digestion and water extractions show higher concentrations in shell ash for most parameters. Calcite is the dominant crystalline compound in this ash (95.6 %), followed by aragonite. Adsorption/desorption trials were performed for mussel shell ash and for a waste mixture including shell ash, sewage sludge and wood ash, showing the following percentage adsorptions: Hg(II) >94 %, As(V) >96 % and Cr(VI) between 11 and 30 % for shell ash; Hg(II) >98 %, As(V) >88 % and Cr(VI) between 30 and 88 % for the waste mixture. Hg and As desorption was <5 % for both shell ash and the waste mixture, while Cr desorption was between 92 and 45 % for shell ash, and between 19 and 0 % for the mixture. In view of that, mussel shell ash and the mixture including shell ash, sewage sludge and wood ash could be useful for Hg(II) and As(V) removal.