Evaluation of Solidified Wastewater Treatment Sludge as a Potential SCM in Pervious Concrete Pavements.

Waste and recycled materials have recently been used in the construction industry to comply with the principles of circular economy and sustainable development. The aim of this paper is to examine the potentials of solidified wastewater treatment sludge (SWWTS) as a supplementary cementitious material (SCM) in the production of lightweight pervious concrete pavers (LWPCP) suitable for pedestrian trails and rooftops (green) that comply with EU standards. Detailed characterization of SWWTS was performed, in order to understand its properties related to application as SCM, which led to the conclusion that it may be applied only as a filler, having 89.5% of Ca(OH)2. After thorough characterization, LWPCP samples were prepared and testing of physical and mechanical properties was conducted. The research showed that partial replacement of cement with SWWTS led to the decrease of all mechanical properties, ranging between 3.91 and 5.81 MPa for compressive strength and 0.97 to 1.23 MPa for flexural strength. However, all of the investigated mixtures showed a value higher than 3.5 MPa, which was defined as the lowest compressive strength in the range of pervious concrete properties. The addition of SWWTS led to a slight decrease in bulk density of the mixtures and an increase in water absorption. This could be explained by the reduction in hydration products that would fill in the micropores of the matrix, since SWWTS showed no pozzolanic reactivity. Pore sizes that prevail in the tested binder matrices are in accordance with the results measured on ordinary pervious concrete (the largest fraction of pores had a diameter between 0.02 and 0.2 µm). Low thermal conductivity nominates produced pavers as potential rooftop elements.

Build-up and characterisation of pollutants on urban impervious surfaces.

This paper presents the results of the investigation of pollutant build-up on impervious surfaces of a parking lot in Belgrade, Serbia during the summer months. Contaminant build-up was found to be greater on asphalt surfaces directly exposed to vehicular traffic than on concrete walkways. The difference in the amounts of accumulated pollutants between asphalt and concrete were significant: for total solids (TS), total suspended solids (TSS), chemical oxygen demand (COD), heavy metals and total phosphorus (TP) accumulations were two to three times higher, while only 30% higher for total nitrogen (TN) and anions. Build-up of most of the measured parameters was best described by power functions. The highest surface loads were found for solids, COD, iron and zinc. A strong correlation was found between turbidity, TS, TSS, COD, heavy metals and phosphorus, while conductivity, nitrates and nitrites were weakly correlated to other parameters.

The removal of Zn2+, Pb2+, and As(V) ions by lime activated fly ash and valorization of the exhausted adsorbent.

This study focuses on the use of raw fly ash (FA) and modified fly ash - activated by lime (MFA), as effective and low-cost adsorbents for the removal of heavy metals (Zn2+, Pb2+ and As(V)), followed by the revalorization of the exhausted adsorbent. The granulometric, elemental analysis, point of zero charge (pHPZC), radiochemical and structural characterization were conducted using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) and gamma spectrometry techniques. The optimal conditions and key factors influencing the adsorption process were assessed using the response surface method (RSM). The adsorption capacity of the MFA adsorbent for Zn2+, Pb2+ and As(V) removal, calculated by the Langmuir model, was found to be 33.13, 26.06, and 29.71 mg g-1, respectively. The kinetic and thermodynamic parameters indicated that the adsorption process is spontaneous and endothermic. Due to their low desorption potential of the exhausted adsorbents, their effective reuse was established to be feasible. For this reason, the valorization of this material as an additive in construction materials was thereafter studied, where testing its toxicity leaching (TCLP) as well as the mechanical properties of construction material containing exhausted MFA confirmed its safe use. Hence, this study points to a possible "two-in-one" reuse of coal ash, initially as an adsorbent and later as an additive in a construction material.

Natural sorbents modified by divalent Cu2+- and Zn2+- ions and their corresponding antimicrobial activity.

The objective of this study was to investigate the modification of materials used in wastewater treatment for possible antimicrobial application(s). Granulated activated carbon (GAC) and natural clinoptilolite (CLI) were activated using Cu2+- and Zn2+- ions and the disinfection ability of the resulting materials was tested. Studies of the sorption and desorption kinetics were performed in order to determine and clarify the antimicrobial activity of the metal-activated sorbents. The exact sorption capacities of the selected sorbents, GAC and CLI, activated through use of Cu2+- ions, were 15.90 and 3.60mg/g, respectively, while for the materials activated by Zn2+- ions, the corresponding capacities were 14.00 and 4.72mg/g,. The desorption rates were 2 and 3 orders of magnitude lower than their sorption efficacy for the Cu2+-, and Zn2+-activated sorbents, respectively. The intermediate sorption capacity and low desorption rate indicated that the overall antimicrobial activity of the metal-modified sorbents was a result of metal ions immobilized onto surface sites. The effect of antimicrobial activity of free ions desorbed from the metal-activated surface may thus be disregarded. The antimicrobial activities of Cu/GAC, Zn/GAC, Cu/CLI and Zn/CLI were also tested against Escherichia coli, Staphylococcus aureus, and Candida albicans. After 15min exposure, the highest levels of cell inactivation were obtained through the Cu/CLI and the Cu/GAC against E. coli, 100.0 and 98.24%, respectively. However, for S. aureus and yeast cell inactivation, all Cu2+- and Zn2+-activated sorbents proved to be unsatisfactory. A characterization of the sorbents was performed by X-ray diffraction (XRD), X-ray photo electron spectroscopy (XPS), and field emission scanning electron microscopy (FE-SEM). A concentration of the adsorbed and released ions was determined by inductively coupled plasma-optical emission spectroscopy (ICP-OES) and mass spectrometry (ICP-MS). The results showed that the antimicrobial performance of the activated sorbents depended on the surface characteristics of the material, which itself designates the distribution and the bioavailability of the activating agent.

Further insight into the mechanism of heavy metals partitioning in stormwater runoff.

Various particles and materials, including pollutants, deposited on urban surfaces are washed off by stormwater runoff during rain events. The interactions between the solid and dissolved compounds in stormwater runoff are phenomena of importance for the selection and improvement of optimal stormwater management practices aimed at minimizing pollutant input to receiving waters. The objective of this research was to further investigate the mechanisms responsible for the partitioning of heavy metals (HM) between the solid and liquid phases in urban stormwater runoff. The research involved the collection of samples from urban asphalt surfaces, chemical characterization of the bulk liquid samples, solids separation, particle size distribution fractionation and chemical and physico-chemical characterization of the solid phase particles. The results revealed that a negligible fraction of HM was present in the liquid phase (less than 3% by weight), while there was a strong correlation between the total content of heavy metals and total suspended solids. Examinations of surface morphology and mineralogy revealed that the solid phase particles consist predominantly of natural macroporous materials: alpha quartz (80%), magnetite (11.4%) and silicon diphosphate (8.9%). These materials have a low surface area and do not have significant adsorptive capacity. These materials have a low surface area and do not have significant adsorptive capacity. The presence of HM on the surface of solid particles was not confirmed by scanning electron microscopy and energy dispersive X-ray microanalyses. These findings, along with the results of the liquid phase sample characterization, indicate that the partitioning of HM between the liquid and solid phases in the analyzed samples may be attributed to precipitation processes.

A new approach in regression analysis for modeling adsorption isotherms.

Numerous regression approaches to isotherm parameters estimation appear in the literature. The real insight into the proper modeling pattern can be achieved only by testing methods on a very big number of cases. Experimentally, it cannot be done in a reasonable time, so the Monte Carlo simulation method was applied. The objective of this paper is to introduce and compare numerical approaches that involve different levels of knowledge about the noise structure of the analytical method used for initial and equilibrium concentration determination. Six levels of homoscedastic noise and five types of heteroscedastic noise precision models were considered. Performance of the methods was statistically evaluated based on median percentage error and mean absolute relative error in parameter estimates. The present study showed a clear distinction between two cases. When equilibrium experiments are performed only once, for the homoscedastic case, the winning error function is ordinary least squares, while for the case of heteroscedastic noise the use of orthogonal distance regression or Margart's percent standard deviation is suggested. It was found that in case when experiments are repeated three times the simple method of weighted least squares performed as well as more complicated orthogonal distance regression method.

Review: the approaches for estimation of limit of detection for ICP-MS trace analysis of arsenic.

The analytical properties of an analytical method must be evaluated through validation protocols. Beside specificity and/or selectivity, linearity of calibration, repeatability and accuracy, the most important parameters are: LOD (limit of detection) and LOQ (limit of quantification). Through these limits, it is possible to define the smallest concentration of analyte that can be reliably detected and quantified. To establish these limits, an analyst should apply several estimation methods and test a large number of sample replicates. It is difficult to make a compromise between complex statistical programs and the simple analytical demand to have reliable analytical parameters. The differences and equivalency of estimation methods and approaches for analytical limits could be overcome by an experimental comparison. In this paper, the focus is the LOD of inductively coupled plasma-mass spectrometry (ICP-MS) measurements employed for the determination of arsenic. The current approaches for the calculation of the LOD are summarized and critically discussed.

Separation and determination of arsenic species in water by selective exchange and hybrid resins.

A simple and efficient method for separation and determination of inorganic arsenic (iAs) and organic arsenic (oAs) in drinking, natural and wastewater was developed. If arsenic is present in water prevailing forms are inorganic acids of As(III) and As(V). oAs can be found in traces as monomethylarsenic acid, MMA(V), and dimethylarsenic acid, DMAs(V). Three types of resins: a strong base anion exchange (SBAE) and two hybrid (HY) resins: HY-Fe and HY-AgCl, based on the activity of hydrated iron oxides and a silver chloride were investigated. It was found that the sorption processes (ion exchange, adsorption and chemisorptions) of arsenic species on SBAE (ion exchange) and HY resins depend on pH values of water. The quantitative separation of molecular and ionic forms of iAs and oAs was achieved by SBAE and pH adjustment, the molecular form of As(III) that exists in the water at pH <8.0 was not bonded with SBAE, which was convenient for direct determination of As(III) concentration in the effluent. HY-Fe resin retained all arsenic species except DMAs(V), which makes possible direct measurements of this specie in the effluent. HY-AgCl resin retained all iAs which was convenient for direct determination of oAs species concentration in the effluent. The selective bonding of arsenic species on three types of resins makes possible the development of the procedure for measuring and calculation of all arsenic species in water. In order to determine capacity of resins the preliminary investigations were performed in batch system and fixed bed flow system. Resin capacities were calculated according to breakthrough points in a fixed bed flow system which is the first step in designing of solid phase extraction (SPE) module for arsenic speciation separation and determination. Arsenic adsorption behavior in the presence of impurities showed tolerance with the respect to potential interference of anionic compounds commonly found in natural water. Proposed method was established performing standard procedures: with external standard, certified reference material and standard addition method. Two analytical techniques: the inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectroscopy-hydride generation (AAS-GH) were comparatively applied for the determination of arsenic in all arsenic species in water. ICP-MS detection limit was 0.2 µg L(-1) and relative standard deviation (RSD) of all arsenic species investigated was between 3.5 and 5.1%.

Determination of inorganic arsenic species in natural waters--benefits of separation and preconcentration on ion exchange and hybrid resins.

A simple method for the separation and determination of inorganic arsenic (iAs) species in natural and drinking water was developed. Procedures for sample preparation, separation of As(III) and As(V) species and preconcentration of the total iAs on fixed bed columns were defined. Two resins, a strong base anion exchange (SBAE) resin and a hybrid (HY) resin were utilized. The inductively-coupled plasma-mass spectrometry method was applied as the analytical method for the determination of the arsenic concentration in water. The governing factors for the ion exchange/sorption of arsenic on resins in a batch and a fixed bed flow system were analyzed and compared. Acidity of the water, which plays an important role in the control of the ionic or molecular forms of arsenic species, was beneficial for the separation; by adjusting the pH values to less than 8.00, the SBAE resin separated As(V) from As(III) in water by retaining As(V) and allowing As(III) to pass through. The sorption activity of the hydrated iron oxide particles integrated into the HY resin was beneficial for bonding of all iAs species over a wide range of pH values from 5.00 to 11.00. The resin capacities were calculated according to the breakthrough points in a fixed bed flow system. At pH 7.50, the SBAE resin bound more than 370 microg g(-1) of As(V) while the HY resin bound more than 4150 microg g(-1) of As(III) and more than 3500 microg g(-1) of As(V). The high capacities and selectivity of the resins were considered as advantageous for the development and application of two procedures, one for the separation and determination of As(III) (with SBAE) and the other for the preconcentration and determination of the total arsenic (with HY resin). Methods were established through basic analytical procedures (with external standards, certified reference materials and the standard addition method) and by the parallel analysis of some samples using the atomic absorption spectrometry-hydride generation technique. The analytical properties of both procedures were similar: the limit of detection was 0.24 microg L(-1), the limit of quantification was 0.80 microg L(-1) and the relative standard deviations for samples with a content of arsenic from 10.00 to 300.0 microg L(-1) ranged from 1.1 to 5.8%. The interference effects of anions commonly found in water and some organic species which can be present in water were found to be negligible. Verification with certified reference materials proved that the experimental concentrations found for model solutions and real samples were in agreement with the certified values.