A systematic review on the bioremediation of metal contaminated soils using biochar and slag: current status and future outlook.

Heavy metals contaminated soils are posing severe threats to food safety worldwide. Heavy metals absorbed by plant roots from contaminated soils lead to severe plant development issues and a reduction in crop yield and growth. The global population is growing, and the demand for food is increasing. Therefore, it is critical to identify soil remediation strategies that are efficient, economical, and environment friendly. The use of biochar and slag as passivators represents a promising approach among various physicochemical and biological strategies due to their efficiency, cost-effectiveness, and low environmental impact. These passivators employ diverse mechanisms to reduce the bioavailability of metals in contaminated soils, thereby improving crop growth and productivity. Although studies have shown the effectiveness of different passivators, further research is needed globally as this field is still in its early stages. This review sheds light on the innovative utilization of biochar and slag as sustainable strategies for heavy metal remediation, emphasizing their novelty and potential for practical applications. Based on the findings, research gaps have been identified and future research directions proposed to enable the full potential of passivators to be utilized effectively and efficiently under controlled and field conditions.

NPA-Cu2+ Complex as a Fluorescent Sensing Platform for the Selective and Sensitive Detection of Glyphosate.

Glyphosate is a highly effective, low-toxicity, broad-spectrum herbicide, which is extensively used in global agriculture to control weeds and vegetation. However, glyphosate has become a potential threat to human and ecosystem because of its excessive usage and its bio-concentration in soil and water. Herein, a novel turn-on fluorescent probe, N-n-butyl-4-(3-pyridin)ylmethylidenehydrazine-1,8-naphthalimide (NPA), is proposed. It efficiently detected Cu2+ within the limit of detection (LOD) of 0.21 µM and displayed a dramatic turn-off fluorescence response in CH3CN. NPA-Cu2+ complex was employed to selectively and sensitively monitor glyphosate concentrations in real samples accompanied by a fluorescence turn-on mode. A good linear relationship between NPA and Cu2+ of glyphosate was found in the range of 10-100 µM with an LOD of 1.87 µM. Glyphosate exhibited a stronger chelation with Cu2+ than NPA and the system released free NPA through competitive coordination. The proposed method demonstrates great potential in quantitatively detecting glyphosate in tap water, local water from Songhua River, soil, rice, millet, maize, soybean, mung bean, and milk with mild conditions, and is a simple procedure with obvious consequences and no need for large instruments or pretreatment.

Automated Solid-Phase Microextraction and Negative Chemical Ionization GC-MS for the Measurement of Synthetic Pyrethroids.

Synthetic pyrethroids are frequently detected as trace contaminants in sediment and natural waters. Because of the importance of measuring both total and freely available concentrations for ecotoxicity evaluations, solid-phase microextraction (SPME) combined with gas chromatography-mass spectrometry using negative chemical ionization (NCI-GC-MS) was investigated as an analytical technique. Automated SPME-NCI-GC-MS quantification of freely dissolved (and thus potentially bioavailable) pyrethroids in aqueous samples containing dissolved organic matter (DOM) was successfully applied. The introduction of stable isotope-labeled pyrethroid calibration standards into the water sample allows for the simultaneous determination of total concentrations. Because pyrethroids adsorb rapidly to container walls (especially in calibration standard solutions without DOM) it was necessary to develop a technique to minimize the resulting time-dependent losses from calibration standard solutions in autosampler vials as they await analysis. A staggered preparation of these analytical calibration standards immediately prior to analysis was shown to ameliorate this problem. The developed method provides accurate and reproducible results for aqueous samples containing a range of dissolved organic matter concentrations (e.g., sediment pore water or sediment/water mixtures) and yields practical benefits in comparison to conventional analysis methods, such as reduced sample volume requirements, reduced solvent consumption, and fewer sample manipulations, and makes simultaneous measurements of freely dissolved/bioavailable pyrethroids and total pyrethroids possible.

Zeolitic imidazolate framework-8 decorated with gold nanoparticles for solid-phase extraction of neonicotinoids in agricultural samples.

A composite built with aminated zeolitic imidazolate framework and gold nanoparticles (AuNPs) for solid-phase extraction (SPE) of neonicotinoids in agricultural samples is presented. The composite was prepared through the assembly of AuNPs onto the surface of metal-organic framework based on the strong interaction between the amino group and AuNP. These metallic surfaces provided additional interactions based on the affinity of amino and cyano groups present in the target compounds. The composite was characterized by scanning electron microscopy, powder X-ray diffraction, Fourier-transform infrared spectroscopy, and surface area measurements. Regarding the SPE protocol, several parameters that can influence the extraction performance were optimized, such as sample volume or composition of elution solvent, among others. After elution, the analytes were determined via HPLC with diode-array detection. Under the selected conditions, satisfactory recoveries of five pesticides (thiamethoxan, clothianidin, imidacloprid, acetamiprid, and thiacloprid) were obtained (between 80 and 110%) in real samples, whereas the limits of detection ranged from 0.019 to 0.041 µg L-1 in aqueous samples and 0.3 to 0.8 µg g-1 in solid samples.

Ultrasound-assisted soil washing processes for the remediation of heavy metals contaminated soils: The mechanism of the ultrasonic desorption.

Ultrasound-assisted soil washing processes were investigated for the removal of heavy metals (Cu, Pb, and Zn) in real contaminated soils using HCl and EDTA. The ultrasound-assisted soil washing (US/Mixing) process was compared with the conventional soil washing (Mixing) process based on the mechanical mixing. High removal efficiency (44.8% for HCl and 43.2% for EDTA) for the metals was obtained for the most extreme conditions (HCl 1.0 M or EDTA 0.1 M and L:S = 10:1) in the Mixing process. With the aide of ultrasound, higher removal efficiency (57.9% for HCl and 50.0% for EDTA) was obtained in the same extreme conditions and similar or higher removal efficiency (e.g., 54.7% for HCl 0.5 M and L:S = 10:1 and 50.5% for EDTA 0.05 M and L:S = 5:1) was achieved even in less extreme conditions (lower HCl or EDTA concentration and L:S ratio). Therefore, it was revealed that the US/Mixing was advantageous over the conventional Mixing processes in terms of metal removal efficiency, consumption of chemicals, amount of generated washing leachate, and volume/size of washing reactor. In addition, the heavy metals removal was enhanced for the smaller soil particles in the US/Mixing process. It was due to more violent movement of smaller particles in slurry phase and more violent sonophysical effects. In order to understand the mechanism of ultrasonic desorption, the desorption test was conducted using the paint-coated beads with three sizes (1, 2, and 4 mm) for the free and attached conditions. It was found that no significant desorption/removal of paint from the beads was observed without the movement of beads in the water including floatation, collision, and scrubbing. Thus, it was suggested that the simultaneous application of the ultrasound and mechanical mixing could enhance the physical movement of the particles significantly and the very high removal/desorption could be attained.

Toxic metal phytoextraction potential and health-risk parameters of some cultivated plants when grown in metal-contaminated river sediment of Danube, near an industrial town.

Toxic metal phytoextraction potential of some higher plants, the white mustard (Sinapis alba L.), perennial rye grass (Lolium perenne L.) and also two cultivated plants, as green pea (Pisum sativum L. var. Rajnai törpe), radish (Raphanus sativus L. var. Szentesi óriás vaj), was studied in a field experiment, along the river Danube in close vicinity of an industrial town, Dunaújváros, Hungary. Soil/sediment and the various plant organs (leaves, stems and roots) were assessed for the contamination with some potentially toxic elements (PTE), such as the cadmium (Cd), nickel (Ni), copper (Cu), and zinc (Zn). It was found that Cd and Ni concentration was below, while the Cu and Zn elements were above the Hungarian permissible limits in each of the studied soil/sediment samples. Bioconcentration factor (BAF) was less than 1 in the shoot biomass of test plant samples and followed the order of Cu > Zn > Cd and Ni. Phytoremediation potential of selected test plants was found to be rather limited. The translocation factor (TF) was more than 1 for Cu and Zn elements, at each test plants. Cadmium was translocated into the leaves in case of the radish, only. Considering of the potential human daily intake of metals (DIM), it was less than 1 both for the adults and for the children. Health risk index (HRI) values of children, however, were higher than 1 for the Cd in case of radish, and for Zn and Cu in case of the pea. Results suggest that consumption of these plants grown in gardens of contaminated sediments can result in some risks for citizens in the industrial town of Dunaújváros. Further studies are required to identify appropriate plants with greater toxic metal phytoextraction potential.

Response of bacterial and fungal communities to high petroleum pollution in different soils.

Petroleum pollution of soils is a major environmental problem. Soil microorganisms can decompose a significant fraction of petroleum hydrocarbons in soil at low concentrations (1-5%). This characteristic can be used for soil remediation after oil pollution. Microbial community dynamics and functions are well studied in cases of moderate petroleum pollution, while cases with heavy soil pollution have received much less attention. We studied bacterial and fungal successions in three different soils with high petroleum contents (6 and 25%) in a laboratory experiment. The proportion of aliphatic and aromatic compounds decreased by 4-7% in samples with 6% pollution after 120 days of incubation but remained unchanged in samples with 25% hydrocarbons. The composition of the microbial community changed significantly in all cases. Oil pollution led to an increase in the relative abundance of bacteria such as Actinobacteria and the candidate TM7 phylum (Saccaribacteria) and to a decrease in that of Bacteroidetes. The gene abundance (number of OTUs) of oil-degrading bacteria (Rhodococcus sp., candidate class TM7-3 representative) became dominant in all soil samples, irrespective of the petroleum pollution level and soil type. The fungal communities in unpolluted soil samples differed more significantly than the bacterial communities. Nonmetric multidimensional scaling revealed that in the polluted soil, successions of fungal communities differed between soils, in contrast to bacterial communities. However, these successions showed similar trends: fungi capable of lignin and cellulose decomposition, e.g., from the genera Fusarium and Mortierella, were dominant during the incubation period.

Speciation of Zn and Cu in Technosol and evaluation of a sequential extraction procedure using XAS, XRD and SEM-EDX analyses.

Metal speciation, linked directly to bioaccessibility and lability, is a key to be considered when assessing associated human and environmental health risks originated from anthropogenic activities. To identify the Zn and Cu speciation in the highly contaminated, technogenically transformed soils (Technosol) from the impact zone near the industrial sludge reservoirs of chemical plant (Siverskyi Donets River floodplain, southern Russia), the validity of the BCR sequential extraction procedure using the X-ray absorption fine-structure and X-ray powder diffraction (XRD) analyses was examined after each of the three stages. After the removal of exchange and carbonate-bonded Zn and Cu compounds from Technosol (first stage of extraction), the resulting residual soil showed enrichment in a great diversity of metal compounds, primarily with Me-S and Me-O bonds. The number of compounds with a higher solubility decreased at the subsequent stages of extraction. In the residual soil left over after extracting the first and second fractions, the dominant Zn-S bond appeared as würtzite (hexagonal ZnS) that made up more than 50%, while the Cu-S bond was almost completely represented only by chalcocite (Cu2S). The XRD analysis revealed the authigenic minerals of metals with S: sphalerite (cubic ZnS), würtzite (hexagonal ZnS), covellite (CuS) and bornite (Cu5FeS4). The scanning electron microscopy data confirmed that würtzite was the dominant form of Me with sulfur-containing and carbonate-containing minerals. The Zn-S bond was the main component (57%), whereas the Cu-O bond was dominant in the residual fraction (the fraction after the third-stage extraction). The results revealed that the composition of the residual fractions might include some of the most stable and hard-to-recover metal compounds of technogenic origin. Thus, the application of the novel instrumental methods, coupled with the chemical fractionation, revealed the incomplete selectivity of the extractants in the extraction of Zn and Cu in long-term highly contaminated soils.

About plant species potentially promising for phytoextraction of large amounts of toxic trace elements.

There is no information yet about plant species capable of accumulating many different metals/metalloids. The plants feasible for phytoremediation aims must grow fast, have high biomass, deep roots, and should accumulate and tolerate a range of toxicants in their aerial parts. In our research, greenhouse and field experiments have been performed to investigate accumulation and tolerance of not well-studied trace elements such as Br, Eu, Sc, Th (and also U) in couch grass and wheat. We compared bioaccumulation abilities of the plants with those of some other plant species grown under the same conditions. Additionally, we tested the effects of inoculation of seeds with Cellulomonas bacteria on phytoextraction of the trace elements from contaminated soils. For determination of elements, we used neutron activation analysis and ICP-MS. It was found that couch grass and wheat can grow in heavily contaminated soils and accumulate different toxic trace elements to levels that exceed physiological requirements typical for most plant species. Infection of seeds with bacteria resulted in a significant increase in the uptake of various trace elements and their translocation to upper plant parts. The use of couch grass and/or wheat, either alone or in combination with microorganisms, is a promising way to phytoextract metals/metalloids from contaminated soils.

Controls on δ26Mg variability in three Central European headwater catchments characterized by contrasting bedrock chemistry and contrasting inputs of atmospheric pollutants.

Magnesium isotope ratios (26Mg/24Mg) can provide insights into the origin of Mg pools and fluxes in catchments where Mg sources have distinct isotope compositions, and the direction and magnitude of Mg isotope fractionations are known. Variability in Mg isotope compositions was investigated in three small, spruce-forested catchments in the Czech Republic (Central Europe) situated along an industrial pollution gradient. The following combinations of catchment characteristics were selected for the study: low-Mg bedrock + low Mg deposition (site LYS, underlain by leucogranite); high-Mg bedrock + low Mg deposition (site PLB, underlain by serpentinite), and low-Mg bedrock + high Mg deposition (site UDL, underlain by orthogneiss). UDL, affected by spruce die-back due to acid rain, was the only investigated site where dolomite was applied to mitigate forest decline. The δ26Mg values of 10 catchment compartments were determined on pooled subsamples. At LYS, a wide range of δ26Mg values was observed across the compartments, from -3.38 ‰ (bedrock) to -2.88 ‰ (soil), -1.48% (open-area precipitation), -1.34 ‰ (throughfall), -1.19 ‰ (soil water), -0.99 ‰ (xylem), -0.95 ‰ (needles), -0.82 ‰ (bark), -0.76 ‰ (fine roots), and -0.76 ‰ (runoff). The δ26Mg values at UDL spanned 1.32 ‰ and were thus less variable, compared to LYS. Magnesium at PLB was isotopically relatively homogeneous. The δ26Mg systematics was consistent with geogenic control of runoff Mg at PLB. Mainly atmospheric/biological control of runoff Mg was indicated at UDL, and possibly also at LYS. Our sites did not exhibit the combination of low-δ26Mg runoff and high-δ26Mg weathering products (secondary clay minerals) reported from several previously studied sites. Six years after the end of liming at UDL, Mg derived from dolomite was isotopically undetectable in runoff.

Determination of Total Hydrocarbons in Contaminated Soil with "Thin Layer Sorptive Extraction Coupled with Attenuated Total Reflectance-Fourier Transform Infrared Spectroscopy".

Soil analysis using infrared spectroscopy has been proposed as an alternative to conventional soil analysis to detect soil contamination. This study therefore aims to develop an innovative, in situ, rapid, precise, and inexpensive method that is easy to implement in order to assess soil contamination with hydrocarbons. This work describes the development and validation of a new extraction method by thin-layer sorptive extraction and attenuated total reflectance-Fourier transform infrared spectroscopy (TLSE-ATR-FTIR). First, this method allows the preconcentration of thermodesorbed pollutants on a polymer thin film and then, their quantification by ATR-FTIR using a standard addition method. A five factor fractional factorial design was used to identify the most significant factors impacting the analysis. These factors include soil texture, total organic carbon (TOC), humidity, and concentrations of contaminants. The results showed that TOC, nature (clay, sandy, and loamy) of the soil, and the concentration of pollutants can affect the infrared absorbance. The analytical method has been validated by verifying the different performance criteria such as linearity, accuracy, precision, and quantitation limit. The comparison of the results obtained by TLSE-ATR-FTIR to the results of conventional analyses carried out by accredited laboratories confirms that the use of the proposed method can become an effective alternative to the current methods for the determination of the total hydrocarbons in soils.

Desorption process and morphological analysis of real polycyclic aromatic hydrocarbons contaminated soil by the heterogemini surfactant and its mixed systems.

Surfactant-enhanced remediation (SER) is an efficient and low-cost technology for polycyclic aromatic hydrocarbons (PAHs) contaminated sites. This study assessed the desorption processes and effects of Heterogemini surfactant (Dodecyldimethylammonium bromide/tetradecyldimethylammonium bromide, DBTB), two traditional surfactants (Hexadecyl trimethyl ammonium bromide, CTAB; Sorbitan monolaurate, Span 20) and their mixed systems on the real PAHs-contaminated soil from an abandoned coking plant, as well they were analyzed micro morphologically. DBTB had greater desorption capability for PAHs and favorable interaction with the traditional surfactants confirmed by reaction parameters ßm and Gibbs. Whether for total PAHs (TPAHs) or different molecular weight PAHs, the mixed system Span 20/DBTB had larger molar solubilization ratio (MSR) and partition coefficient (Km) than CTAB/DBTB, the highest desorption rate for TPAHs reaching 68.83%. Additionally, microscopic morphology showed micelles of Span 20/DBTB were more dispersed and formed strings easily, explaining its good desorption capability. What resulted demonstrated the feasibility of DBTB, a novel Heterogemini surfactant, and its mixed systems remediating PAHs-contaminated soil of abandoned industrial site.

Effect of soil type on heavy metals removal in bioelectrochemical system.

Microbial fuel cell (MFC) technology is widely used to remediate heavy metal pollution of soil, and the applicability of soils with different physical and chemical properties under micro-electric field has not been studied. In this study, copper was effectively removed in four typical soil-filled MFCs. The removal efficiencies of copper from closed-circuit MFCs filled with paddy, red, black and alluvial soils were 2.9, 1.50, 3.48 and 3.40 times higher than those in the open-circuit control group, respectively. However, the contributions of electromigration and diffusion mechanisms were different under different soil types. The greatest copper removal (19.3 ± 0.8%) was achieved based on electromigration of the electric field inside the paddy soil MFC in 63 days, while the greatest copper removal (25 ± 2%) was achieved under the action of diffusion mechanism inside the red soil MFC. According to redundancy analysis, the removal of copper by electromigration was positively correlated with electricity generation performance and acid extractable Cu content, whereas copper removal based on diffusion was positively related to soil pore volume and acid extractable Cu content. The cation exchange capacity and total organic carbon of soil were negatively correlated with the acid extractable Cu content, and electrical conductivity of soil was positively correlated with the MFC electricity generation performance. Furthermore, the directional movement of protons under an electric field alleviated the issue of soil acidification caused by citric acid.

Study on the preparation of the hierarchical porous CX-TiO2 composites and their selective degradation of PHE solubilized in soil washing eluent.

A series of CX-TiO2(Carbon Xerogel- TiO2) composites with a hierarchical porous structure were obtained through the sol-gel method followed by drying and carbonization, and have been applied to treating solubilizing wastewater containing a high concentration of phenanthrene (PHE). The characterizations demonstrated that the CX-TiO2 exhibits a hierarchical porous structure, with particles of carbon and P25 being uniformly in the matrix. Removal efficiency of CX-TiO2 on PHE in soil washing eluent (SWE) were evaluated under ultraviolet (UV) irradiation or dark condition, and P25 was employed as the reference. The results revealed that CX-TiO2(0.2) had the best removal effect on PHE, with the efficiency as high as 97.8% under UV illumination within 15 h. It demonstrated that in the process of PHE removal by CX-TiO2 whether it was under UV illumination or not, the adsorption plays a dominant role in the early stage. The kinetic behavior of PHE adsorption was fitted using the pseudo-first-order and pseudo-second-order, and Langmuir model and Freundlich models were applied to describe the PHE adsorption isotherms. The results indicating that it was a chemical adsorption process, which was influenced by the interaction between PHE and CX-TiO2, and PHE is adsorbed on the interface of CX-TiO2(0.2) in a single layer form, instead of agglomerating in the admicelle. A possible mechanism of removal of solubilized PHE in SWE was speculated, in which both hierarchical porous structure and appropriate micropores size of CX-TiO2 were indispensable to the selective adsorption and degradation of PHE. Recycling performance certificated that the selective removal efficiency of PHE could still reach 82.09% after five recycles. Thus the excellent performance testified that the CX-TiO2 have great potential in treating SWE containing solubilized PAHs.

Surface-enhanced Raman Spectroscopy Coupled with Dispersive Solid-phase Extraction for the Rapid Detection of Tricyclazole Residues in Rice and Brassica campestris L. ssp. chinensis var. utilis Tsen.

An efficient methodology has been developed to determine the tricyclazole residue in matrix based on surface-enhanced Raman scattering (SERS) coupled with dispersible matrix solid-phase extraction. After pretreatment and test conditions optimization, peaks at 1373 and 1317 cm-1 in the SERS spectrum were respectively selected as quantitative peaks for rice and Brassica campestris L. ssp. chinensis var. utilis Tsen, respectively. The matrix standard curve-external standard method was used to quantitatively conduct a statistical analysis. The correlation between the quantitative peak response and tricyclazole concentration showed a significant linear relationship with a correlation coefficient of R2 > 0.99. The lowest spiked concentration was determined to be the quantitative limit that was below the maximum residue limits of tricyclazole. This study provides a sensitive, stable and rapid approach for the analysis of tricyclazole in above matrix via SERS, and it will be a useful complement to the quantitative analysis of tricyclazole in a complex matrix.

Synthetic biology approaches towards the recycling of metals from the environment.

Metals are a finite resource and their demand for use within existing and new technologies means metal scarcity is increasingly a global challenge. Conversely, there are areas containing such high levels of metal pollution that they are hazardous to life, and there is loss of material at every stage of the lifecycle of metals and their products. While traditional resource extraction methods are becoming less cost effective, due to a lowering quality of ore, industrial practices have begun turning to newer technologies to tap into metal resources currently locked up in contaminated land or lost in the extraction and manufacturing processes. One such technology uses biology for the remediation of metals, simultaneously extracting resources, decontaminating land, and reducing waste. Using biology for the identification and recovery of metals is considered a much 'greener' alternative to that of chemical methods, and this approach is about to undergo a renaissance thanks to synthetic biology. Synthetic biology couples molecular genetics with traditional engineering principles, incorporating a modular and standardised practice into the assembly of genetic parts. This has allowed the use of non-model organisms in place of the normal laboratory strains, as well as the adaption of environmentally sourced genetic material to standardised parts and practices. While synthetic biology is revolutionising the genetic capability of standard model organisms, there has been limited incursion into current practices for the biological recovery of metals from environmental sources. This mini-review will focus on some of the areas that have potential roles to play in these processes.

Robust Matrix Effect-Free Method for Simultaneous Determination of Legacy and Emerging Per- and Polyfluoroalkyl Substances in Crop and Soil Matrices.

Increasing use of emerging per- and polyfluoroalkyl substances (PFASs) has caused extensive concerns around the world. Effective detection methods to trace their pollution characteristics and environmental behaviors in complex soil-crop systems are urgently needed. In this study, a reliable and matrix effect (ME)-free method was developed for simultaneous determination of 14 legacy and emerging PFASs, including perfluorooctanoic acid, perfluorooctane sulfonate, 6 hydrogenous PFASs, 3 chlorinated PFASs, and 3 hexafluoropropylene oxide homologues, in 6 crop (the edible parts) and 5 soil matrices using ultrasonic extraction combined with solid-phase extraction and ultraperformance liquid chromatography-mass spectrometry (MS)/MS. The varieties of extractants and cleanup cartridges, the dosage of ammonia hydroxide, and the ME were studied to obtain an optimal pretreatment procedure. The developed method had high sensitivity and accuracy with satisfactory method detection limits (2.40-83.03 pg/g dry weight) and recoveries (72-117%) of all target analytes in matrices at five concentrations, that is, 0.1, 1, 10, 100, and 1000 ng/g. In addition, the ME of this method (0.82-1.15) was negligible for all PFASs, even considering 11 different matrices. The successful application of the ME-free method to simultaneously determine the legacy and emerging PFASs in crop and soil samples has demonstrated its excellent practicability for monitoring emerging PFASs in soil-crop systems.

Effect of Soil Washing Solutions on Simultaneous Removal of Heavy Metals and Arsenic from Contaminated Soil.

In this study, we investigated the feasibility of using a solution of sulfuric acid and phosphoric acid as an extraction method for soil-washing to remove Cu, Pb, Zn, and As from contaminated soil. We treated various soil particles, including seven fraction sizes, using sulfuric acid. In addition, to improve Cu, Pb, Zn, and As removal efficiencies, washing agents were compared through batch experiments. The results showed that each agent behaved differently when reacting with heavy metals (Cu, Pb, and Zn) and As. Sulfuric acid was more effective in extracting heavy metals than in extracting As. However, phosphoric acid was not effective in extracting heavy metals. Compared with each inorganic acid, As removal from soil by washing agents increased in the order of sulfuric acid (35.81%) < phosphoric acid (62.96%). Therefore, an enhanced mixture solution using sulfuric acid and phosphoric acid to simultaneously remove heavy metals and As from contaminated soils was investigated. Sulfuric acid at 0.6 M was adopted to combine with 0.6 M phosphoric acid to obtain the mixture solution (1:1) that was used to determine the effect for the simultaneous removal of both heavy metals and As from the contaminated soil. The removal efficiencies of As, Cu, Pb, and Zn were 70.5%, 79.6%, 80.1%, and 71.2%, respectively. The combination of sulfuric acid with phosphoric acid increased the overall As and heavy metal extraction efficiencies from the contaminated soil samples. With the combined effect of dissolving oxides and ion exchange under combined washings, the removal efficiencies of heavy metals and As were higher than those of single washings.

Factors affecting pluronic-coated iron oxide nanoparticle binding to petroleum hydrocarbon-impacted sediments.

Effective targeted delivery of nanoparticle agents may enhance the remediation of soils and site characterization efforts. Nanoparticles coated with Pluronic, an amphiphilic block co-polymer, demonstrated targeted binding behaviour toward light non-aqueous phase liquids such as heavy crude oil. Various factors including coating concentration, oil concentration, oil type, temperature, and pH were assessed to determine their effect on nanoparticle binding to heavy crude oil-impacted sandy aquifer material. Nanoparticle binding was increased by decreasing the coating concentration, increasing oil concentration, using heavier oil types, and increasing temperature, while pH over the range of 5-9 was found to have no effect. Nanoparticle transport and binding in columns packed with clean and oily porous media demonstrated the ability for efficient nanoparticle targeted binding. For the conditions explored, the attachment rate coefficient in columns packed with clean sand was 2.10 ± 0.66 × 10-4 s-1; however, for columns packed with oil-impacted sand a minimum attachment rate coefficient of 8.86 ± 0.43 × 10-4 s-1 was estimated. The higher attachment rate for the oil-impacted sand system indicates that nanoparticles may preferentially accumulate to oil-impacted zones present at heterogeneous impacted sites. Simulations were used to demonstrate this hypothesis using the set of parameters generated in this effort. This work contributes to our understanding of the application conditions that are required for efficient targeted binding of nanoparticles to crude-oil impacted porous media.

Simultaneous analysis of multiclass antibiotic residues in complex environmental matrices by liquid chromatography with tandem quadrupole mass spectrometry.

A simultaneous extraction and cleanup method was optimized and validated for the determination of 40 antibiotics from cephalosporin, fluoroquinolone, lincosamide, macrolide, nitroimidazole, quinolone, sulfonamide and tetracycline groups in sediments by liquid chromatography with tandem quadrupole mass spectrometry (LC-MS/MS). The method involved hydration of freeze-dried sediment sample (2.0 g) with 2.5 ml of 0.1 M Na-EDTA McIlvaine buffer and extraction with 5 ml of MeOH and MeCN (1:3 v/v) followed by dispersive solid phase extraction by using 100 mg mix of C18 and PSA (1:2 w/w) and 50 mg MgSO4 prior to LC-MS/MS analysis. The method was validated for 10, 20, 50 and 100 µg/kg spiking levels by using blank sediment sample obtained from a drinking water reservoir according to the guidelines of European Commission Decision (2002) 2002/657/EC. The method produced clean extracts with generally low matrix effect during LC-MS/MS analysis. The mean recoveries ranged between 24-162%, 48-151%, 51-159%, and 50-149% for 10, 20, 50 and 100 µg/kg spiking levels, respectively, with acceptable precision. The analytical method was sensitive enough to achieve 0.01-34.3 µg/kg and 0.03-115 µg/kg limits of detection and quantitation, respectively. The scope of the method was demonstrated by analyzing complex solid environmental matrices (chicken manure, swine manure, poultry feed and soil) spiked at 10, 20, 50 and 100 µg/kg levels. The method was also applied for the antibiotic analysis in samples with incurred residues. Different matrices in the order of the magnitude as sediments < poultry feed < swine manure < soil < chicken manure were detected with the residues of fluoroquinolone, macrolide, sulfonamide and tetracycline antibiotics.