Preparation and characterization of PAA/PVDF membrane-immobilized Pd/Fe nanoparticles for dechlorination of trichloroacetic acid

Poly(vinylidene fluoride) (PVDF) microfiltration (MF) membrane was successfully hydrophilized by coating with a novel hydrophilic layer, which was mainly composed of polyvinyl alcohol (PVA), glutaraldehyde, and polyethylene glycol (PEG). Pd/Fe nanoparticles (NPs) were prepared and immobilized in hydrophilized polyacrylic acid (PAA)/PVDF MF membrane. The unmodified and modified PVDF MF membranes were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FT-IR). The membrane-supported Pd/Fe NPs exhibited high reactivity in the dechlorination of trichloroacetic acid (TCAA). The effects of several important parameters, including Pd content, Pd/Fe NP loading, the preservation time of Pd/Fe NP membrane system on the dechlorination of TCAA were investigated. The stability of Pd/Fe NP membrane system was tested, and the kinetics and product distribution of dechlorination of TCAA by Pd/Fe NP membrane system were discussed.     

Synergistic effect of nickel ions on the coupled dechlorination of trichloroethylene and 2,4-dichlorophenol by Fe/TiO₂ nanocomposites in the presence of UV light under anoxic conditions

The coupled removal of priority pollutants by nanocomposite materials has recently been receiving much attention. In this study, trichloroethylene (TCE) and 2,4-dichlorophenol (DCP) in aqueous solutions were simultaneously removed by Fe/TiO₂ nanocomposites under anoxic conditions in the presence of nickel ions and UV light at 365 nm. Both TCE and DCP were effectively dechlorinated by Fe/TiO₂ nanocomposites, and the pseudo-first-order rate constants (k_obs) for TCE and DCP dechlorination were (1.39 ± 0.05)×10⁻² and (1.08 ± 0.05)×10⁻² h⁻¹, respectively, which were higher than that by nanoscale zerovalent iron alone. In addition, the k_obs for DCP dechlorination was enhanced by a factor of 77 when Fe/TiO₂ was illuminated with UV light for 2 h. Hydrodechlorination was found to be the major reaction pathway for TCE dechlorination, while DCP could undergo reductive dechlorination or react with hydroxyl radicals to produce 1,4-benzoquinone and phenol. TCE was a stronger electron acceptor than DCP, which could inhibit the dechlorination efficiency and rate of DCP during simultaneous removal processes. The addition of nickel ions significantly enhanced the simultaneous photodechlorination efficiency of TCE and DCP under the illumination of UV light. The k_obs values for DCP and TCE photodechlorination by Fe/TiO₂ in the presence of 20-100 μM Ni(II) were 30.4-136 and 13.2-192 times greater, respectively, when compared with those in the dark. Electron spin resonance analysis showed that the photo-generated electron-hole pairs could be effectively separated through Ni ions cycling, leading to the improvement of electron transfer efficiency of TCE and DCP by Fe/TiO₂.     

Removal of diatrizoate with catalytically active membranes incorporating microbially produced palladium nanoparticles

There is an increasing concern about the fate of iodinated contrast media (ICM) in the environment. Limited removal efficiencies of currently applied techniques such as advanced oxidation processes require more performant strategies. The aim of this study was to establish an innovative degradation process for diatrizoate, a highly recalcitrant ICM, by using biogenic Pd nanoparticles as free suspension or immobilized in polyvinylidene fluoride (PVDF) and polysulfone (PSf) membranes. As measured by HPLC-UV, the removal of 20 mg L⁻¹ diatrizoate by a 10 mg L⁻¹ Pd suspension was completed after 4 h at a pH of 10. LC-MS analysis provided evidence for the sequential hydrodeiodination of diatrizoate. Pd did not lose its activity after incorporation in the PVDF and PSf matrix and the highest activity (k_cat = 30.0 ± 0.4 h⁻¹ L g⁻¹ Pd) was obtained with a casting solution of 10% PSf and 500 mg L⁻¹ Pd. Subsequently, water containing 20 mg L⁻¹ diatrizoate was treated in a membrane contactor, in which the water was supplied at one side of the membrane while hydrogen was provided at the other side. In a fed batch configuration, a removal efficiency of 77% after a time period of 48 h was obtained. This work showed that membrane contactors with encapsulated biogenic nanoparticles can be instrumental for treatment of water contaminated with diatrizoate.     

Evaluation of nanoscale zerovalent iron particles for trichloroethene degradation in clayey soils

The longevity and reactivity of nanoscale zerovalent iron (nZVI) and palladized bimetallic particles (BNP) were evaluated in batch and column experiments for remediation of a trichloroethene (TCE)-contaminated plume within a clayey soil from Oak Ridge Reservation (ORR). Comparative studies assessing the viability of BNP and nZVI confirmed that particle behavior is severely affected by clay sediments. Surface morphology and composition analyses using SEM and SEM-energy-dispersive spectroscopy spectrum revealed particle agglomeration through the formation of clay-iron aggregates of greater mass during the early phase of the experiment. Batch study results suggest that TCE degradation in ORR clayey soil follows a pseudo-first-order kinetic model exhibiting reaction rate constants (k) of 0.05-0.24 day^− 1 at varied iron-to-soil ratios. Despite high reactivity in water, BNP were less effective in the site-derived clay sediment with calculated TCE removal efficiencies of 98.7% and 19.59%, respectively.A column experiment was conducted to investigate particle longevity and indicator parameters of the TCE degradation process under flow conditions. It revealed that the TCE removal efficiency gradually declined over the course of the experiment from 86-93% to 51-52%, correlating to a progressive increase in oxidation-reduction potential (ORP) from − 485 to − 250 mV and pH drop from 8.2-8.6 to 7.4-7.5. The rate of nZVI deactivation reaction was found to be a first order with a k_d value of 0.0058 day^− 1. SEM images of residual nZVI revealed heavily agglomerated particles. However, despite widespread oxidation and agglomeration, particles managed to maintain some capacity for oxidation. A quantitative analysis of nZVI deactivation has the potential of predicting nZVI longevity in order to improve the design strategy of TCE remediation.     

Field assessment of carboxymethyl cellulose stabilized iron nanoparticles for in situ destruction of chlorinated solvents in source zones

This study pilot-tested carboxymethyl cellulose (CMC) stabilized zero-valent iron (ZVI) nanoparticles (with a trace amount of Pd catalyst) for in situ destruction of chlorinated ethenes such as perchloroethylene (PCE) and trichloroethylene (TCE) and polychlorinated biphenyls (PCBs) that had been in groundwater for decades. The test site was located in a well-characterized secondary source zone of PCBs and chlorinated ethenes. Four test wells were installed along the groundwater flow direction (spaced 5 ft apart), including one injection well (IW), one up-gradient monitoring well (MW-3) and two down-gradient monitoring wells (MW-1 and MW-2). Stabilized nanoparticle suspension was prepared on-site and injected into the 50-ft deep, unconfined aquifer. Approximately 150 gallons of 0.2 g/L Fe-Pd (CMC = 0.1 wt%, Pd/Fe = 0.1 wt%) was gravity-fed through IW-1 over a 4-h period (Injection #1). One month later, another 150 gallons of 1.0 g/L Fe-Pd (CMC = 0.6 wt%, Pd/Fe = 0.1 wt%) was injected into IW-1 at an injection pressure <5 psi (Injection #2). When benchmarked against the tracer, approximately 37.4% and 70.0% of the injected Fe was detected in MW-1 during injection #1 and #2, respectively, confirming the soil mobility of the nanoparticles through the aquifer, and higher mobility of the particles was observed when the injection was performed under higher pressure. Rapid degradation of PCE and TCE was observed in both MW-1 and MW-2 following each injection, with the maximum degradation being observed during the first week of the injections. The chlorinated ethenes concentrations gradually returned to their pre-injection levels after ∼2 weeks, indicating exhaustion of the ZVI's reducing power. However, the injection of CMC-stabilized nanoparticle and the abiotic reductive dechlorination process appeared to have boosted a long-term in situ biological dechlorination thereafter, which was evidenced by the fact that PCE and TCE concentrations showed further reduction after two weeks. After 596 days from the first injection, the total chlorinated ethenes concentration decreased by about 40% and 61% in MW-1 and MW-2, respectively. No significant long-term reduction of PCB 1242 was observed in MW-1, but a reduction of 87% was evident in MW-2. During the 596 days of testing, the total concentrations of cis-DCE (dichloroethylene) and VC (vinyl chloride) decreased by 20% and 38% in MW-1 and MW-2, respectively. However, the combined fraction of cis-DCE and VC in the total chlorinated ethenes (PCE, TCE, cis-DCE and VC) increased from 73% to 98% and from 62% to 98%, respectively, which supports the notion that biological dechlorination of PCE and TCE was active. It is proposed that CMC-stabilized ZVI-Pd nanoparticles facilitated the early stage rapid abiotic degradation. Over the long run, the existing biological degradation process was boosted with CMC as the carbon source and hydrogen from the abiotic/biotic processes as the electron donor, resulting in the sustained enhanced destruction of the chlorinated organic chlorinated ethenes in the subsurface.     

Dechlorination kinetics of TCE at toxic TCE concentrations: Assessment of different models

The reductive dechlorination of trichloroethene (TCE) in a TCE source zone can be self-inhibited by TCE toxicity. A study was set up to examine the toxicity of TCE in terms of species specific degradation kinetics and microbial growth and to evaluate models that describe this self-inhibition. A batch experiment was performed using the TCE dechlorinating KB-1 culture at initial TCE concentrations ranging from 0.04 mM to saturation (8.4 mM). Biodegradation activity was highest at 0.3 mM TCE and no activity was found at concentrations from 4 to 8 mM. Species specific TCE and cis-DCE (cis-dichloroethene) degradation rates and Dehalococcoides numbers were modeled with Monod kinetics combined with either Haldane inhibition or a log-logistic dose-response inhibition on these rates. The log-logistic toxicity model appeared the most appropriate model and predicts that the species specific degradation activities are reduced by a factor 2 at about 1 mM TCE, respectively cis-DCE. However, the model showed that the inhibitive effects on the time for TCE to ethene degradation are a complex function of degradation kinetics and the initial cell densities of the dechlorinating species. Our analysis suggests that the self-inhibition on biodegradation cannot be predicted by a single concentration threshold without information on the cell densities.     

Optimization of electrochemical dechlorination of trichloroethylene in reducing electrolytes

Electrochemical dechlorination of trichloroethylene (TCE) in aqueous solution is investigated in a closed, liquid-recirculation system. The anodic reaction of cast iron generates ferrous species, creating a chemically reducing electrolyte (negative ORP value). The reduction of TCE on the cathode surface is enhanced under this reducing electrolyte because of the absence of electron competition. In the presence of the iron anode, the performances of different cathodes are compared in a recirculated electrolysis system. The copper foam shows superior capability for dechlorination of aqueous TCE. Electrolysis by cast iron anode and copper foam cathode is further optimized though a multivariable experimental design and analysis. The conductivity of the electrolyte is identified as an important factor for both final elimination efficiency (FEE) of TCE and specific energy consumption. The copper foam electrode exhibits high TCE elimination efficiency in a wide range of initial TCE concentration. Under coulostatic conditions, the optimal conditions to achieve the highest FEE are 9.525 mm thick copper foam electrode, 40 mA current and 0.042 mol L⁻¹ Na₂SO₄. This novel electrolysis system is proposed to remediate groundwater contaminated by chlorinated organic solvents, or as an improved iron electrocoagulation process capable of treating the wastewater co-contaminated with chlorinated compounds.     

Chemisorption of estrone in nylon microfiltration membranes: Adsorption mechanism and potential use for estrone removal from water

Estrone is a representative steroid estrogen contaminant that has been detected in effluents from sewage treatment facilities, as well as in surface and ground waters. Our study shows that estrone can be readily removed from water via a unique chemisorption mechanism using nylon microfiltration membranes. Experiments on a laboratory in-line filtration system showed instant removal of estrone from 200 μg/l aqueous solutions by 0.45-μm nylon membranes (ca. 35 L per m² membrane). Comparisons with 0.45-μm PVDF, PTFE and glass microfiber membranes suggested that the significant estrone adsorption in nylon membrane should be predominately driven by a different mechanism rather than common physical adsorption. Fourier transform infrared spectroscopy study on nylon membranes and a model compound, N-methylacetamide, showed that the significant adsorption originated from the hydrogen bonding between terminal -OH groups on estrone molecules and nucleophile -CO groups in amide groups of nylon 6,6. The saturated nylon membrane showed very low leachability in ambient water, while it could be effectively regenerated in alkaline or ethanol solutions. Preliminary reusability study showed that the membrane maintained a consistent adsorption capacity for estrone during ten cycles of reuse. The chemisorption-based polymeric adsorption may provide a new alternative approach for removing estrone and potentially other trace organic contaminants from water.     

Degradation of soil-sorbed trichloroethylene by stabilized zero valent iron nanoparticles: effects of sorption, surfactants, and natural organic matter

Zero valent iron (ZVI) nanoparticles have been studied extensively for degradation of chlorinated solvents in the aqueous phase, and have been tested for in-situ remediation of contaminated soil and groundwater. However, little is known about its effectiveness for degrading soil-sorbed contaminants. This work studied reductive dechlorination of trichloroethylene (TCE) sorbed in two model soils (a potting soil and Smith Farm soil) using carboxymethyl cellulose (CMC) stabilized Fe-Pd bimetallic nanoparticles. Effects of sorption, surfactants and dissolved organic matter (DOC) were determined through batch kinetic experiments. While the nanoparticles can effectively degrade soil-sorbed TCE, the TCE degradation rate was strongly limited by desorption kinetics, especially for the potting soil which has a higher organic matter content of 8.2%. Under otherwise identical conditions, ∼44% of TCE sorbed in the potting soil was degraded in 30 h, compared to ∼82% for Smith Farm soil (organic matter content = 0.7%). DOC from the potting soil was found to inhibit TCE degradation. The presence of the extracted SOM at 40 ppm and 350 ppm as TOC reduced the degradation rate by 34% and 67%, respectively. Four prototype surfactants were tested for their effects on TCE desorption and degradation rates, including two anionic surfactants known as SDS (sodium dodecyl sulfate) and SDBS (sodium dodecyl benzene sulfonate), a cationic surfactant hexadecyltrimethylammonium (HDTMA) bromide, and a non-ionic surfactant Tween 80. All four surfactants were observed to enhance TCE desorption at concentrations below or above the critical micelle concentration (cmc), with the anionic surfactant SDS being most effective. Based on the pseudo-first-order reaction rate law, the presence of 1×cmc SDS increased the reaction rate by a factor of 2.5 when the nanoparticles were used for degrading TCE in a water solution. SDS was effective for enhancing degradation of TCE sorbed in Smith Farm soil, the presence of SDS at sub-cmc increased TCE degraded by ∼10%. However, effect of SDS on degradation of TCE in the potting soil was more complex. The presence of SDS at sub-cmc decreased TCE degradation by 5%, but increased degradation by 5% when SDS dosage was raised to 5×cmc. The opposing effects were attributed to combined effects of SDS on TCE desorption and degradation, release of soil organic matter and nanoparticle aggregation. The findings strongly suggest that effect of soil sorption on the effectiveness of Fe-Pd nanoparticles must be taken into account in process design, and soil organic content plays an important role in the overall degradation rate and in the effectiveness of surfactant uses.     

Improved hydrophilic property of PES/PEG/MnCO3 blended membranes for synthetic dye separation

Poly(ether sulfone) blended membranes were synthesized with various percentages of manganese carbonate as a surface modifier and poly(ethylene glycol) using a phase inversion technique. Surface characterization was made using scanning electron microscopy, atomic force microscopy and contact angle. The membrane equilibrium water content, porosity and average pore size were measured to evaluate the physical properties of the membrane. Performance of the blended membranes was evaluated in terms of water permeability, antifouling property and dye rejection efficiency. The membrane showed a significant change in surface morphology and hydrophilicity when 3 wt % MnCO₃ was used. Water uptake tests confirmed the enhanced porous nature of the PES/PEG/MnCO₃ blended membranes over the pristine PES membrane. Fouling studies showed that the 3 wt% MnCO₃ blended membrane possesses an impressive 98% flux recovery ratio.     

Removal of phosphorus from solution using biogenic iron oxides

Phosphorus removal by biogenic iron oxides was investigated, providing an initial characterization of a potentially regenerable iron-rich sorbent. The biogenic iron oxides were collected from a wetland ecosystem and were dominated by the sheaths of Leptothrix ochracea. Sorption kinetics followed a pseudo-1st order model (R² = 0.998) with a rate constant of 0.154 ± 0.013 h⁻¹. The Langmuir isotherm adequately described sorption for all samples (R² = 0.923-0.981); the Freundlich model was a better fit for only one of four samples. Maximum phosphorus sorption estimated using the Langmuir parameter ranged from 46.9 ± 2.9 to 165.0 ± 21.2 mg P/g Fe and was similar to other iron-rich substrates. Maximum sorption normalized to total solids ranged from 10.8 ± 0.7 to 39.9 ± 3.2 mg P/g, which represented the highest published values for iron-rich substrates. The high sorption capacity with respect to both iron and solids warrants further evaluation of biogenic iron oxides as a substrate for phosphorus removal.     

Biogenic silver nanoparticles (bio-Ag 0) decrease biofouling of bio-Ag 0/PES nanocomposite membranes

Biofouling is a major problem for the application of membrane technology in water and wastewater treatment. One of the practical strategies to decrease biofouling is the use of advanced anti-biofouling membrane material. In this study, different amounts of biogenic silver nanoparticles (bio-Ag⁰) were embedded in polyethersulfone (PES) membranes, using the phase-inversion method. The effects of the bio-Ag⁰ content on the structure of the membrane and its filtration performance were systematically investigated. The results demonstrated that silver-containing nanostructures were uniformly distributed on membrane surface. Bio-Ag⁰ incorporation slightly increased the hydrophilicity of the PES membrane and increased the permeate flux. The anti-bacterial and anti-biofouling properties of the bio-Ag⁰/PES nanocomposites membrane were tested with pure cultures (Escherichia coli and Pseudomonas aeruginosa) and a mixed culture (an activated sludge bioreactor), respectively. The bio-Ag⁰/PES composite membranes, even with the lowest content of biogenic silver (140 mg bio-Ag⁰ m⁻²), not only exhibited excellent anti-bacterial activity, but also prevented bacterial attachment to the membrane surface and decreased the biofilm formation during a 9 weeks test.     

TiO2 nanoparticles effects on physical, thermal and mechanical properties of self compacting concrete with ground granulated blast furnace slag as binder

In this work, strength assessments and percentage of water absorption of self compacting concrete containing different amounts of ground granulated blast furnace slag and TiO₂ nanoparticles as binder have been investigated. Portland cement was replaced by 45 wt% of ground granulated blast furnace slag and up to 4.0 wt% TiO₂ nanoparticles and the properties of concrete specimens were investigated. TiO₂ nanoparticle as a partial replacement of cement up to 3.0 wt% could accelerate C-S-H gel formation as a result of increased crystalline Ca(OH)₂ amount at the early age of hydration and hence increase strength and improve the resistance to water permeability of concrete specimens. Several empirical relationships have been presented to predict flexural and split tensile strength of the specimens by means of the corresponding compressive strength at a certain age of curing.     

Occurrence of androgens and progestogens in wastewater treatment plants and receiving river waters: Comparison to estrogens

Research has shown that exposure to androgens and progestogens can cause undesirable biological responses in the environment. To date, however, no detailed or direct study of their presence in wastewater treatment plants has been conducted. In this study, nine androgens, nine progestogens, and five estrogens were analyzed in influent and final effluent wastewaters in seven wastewater treatment plants (WWTPs) of Beijing, China. Over a period of three weeks, the average total hormone concentrations in influent wastewaters were 3562 (Wujiacun WWTP)-5400 ng/L (Fangzhuang WWTP). Androgens contributed 96% of the total hormone concentrations in all WWTP influents, with natural androgen (androsterone: 2977 ± 739 ng/L; epiandrosterone: 640 ± 263 ng/L; and androstenedione: 270 ± 132 ng/L) being the predominant compounds. The concentrations of synthetic progestogens (megestrol acetate: 41 ± 25 ng/L; norethindrone: 6.5 ± 3.3 ng/L; and medroxyprogesterone acetate: 6.0 ± 3.2 ng/L) were comparable to natural ones (progesterone: 66 ± 36 ng/L; 17α,20β-dihydroxy-4-progegnen-3-one: 4.9 ± 1.2 ng/L; 21α-hydroxyprogesterone: 8.5 ± 3.0 ng/L; and 17α-hydroxyprogesterone: 1.5 ± 0.95 ng/L), probably due to the wide and relatively large usage of synthetic progestogens in medical therapy. In WWTP effluents, androgens were still the dominant class accounting for 60% of total hormone concentrations, followed by progestogens (24%), and estrogens (16%). Androstenedione and testosterone were the main androgens detected in all effluents. High removal efficiency (91-100%) was found for androgens and progestogens compared with estrogens (67-80%), with biodegradation the major removal route in WWTPs. Different profiles of progestogens in the receiving rivers and WWTP effluents were observed, which could be explained by the discharge of a mixture of treated and untreated wastewater into the receiving rivers.     

Al2O3 nanoparticles in concrete and different curing media

In the present study, the effect of limewater on strength and percentage of water absorption of Al₂O₃ nanoparticles blended concrete has been investigated. Portland cement was partially replaced by Al₂O₃ nanoparticles with the average particle size of 15 nm with different amount and the specimens were cured in water and saturated limewater for specific ages. Utilizing up to 2.0 wt% Al₂O₃ nanoparticles could produce concrete with improved strength and water permeability when the specimens cured in saturated limewater while this content is 1.0 wt% for the specimens cured in tap water. The high action of fine nanoparticles substantially increases the quantity of C-S-H gel. Although the limewater reduces the strength of concrete without nanoparticles when compared with that cured in water, curing the specimens in saturated limewater results in more strengthening gel formation around Al₂O₃ nanoparticles and causes improved permeability together with high strength. In addition, Al₂O₃ nanoparticles are able to act as nanofillers and recover the pore structure of the specimens by decreasing harmful pores. Accelerated peak appearance in conduction calorimetry tests, more weight loss in thermogravimetric analysis and more rapid appearance of peaks related to hydrated products in X-ray diffraction results, all indicate that Al₂O₃ nanoparticles could improve mechanical and physical properties of the specimens.     

Virus disinfection in water by biogenic silver immobilized in polyvinylidene fluoride membranes

The development of innovative water disinfection strategies is of utmost importance to prevent outbreaks of waterborne diseases related to poor treatment of (drinking) water. Recently, the association of silver nanoparticles with the bacterial cell surface of Lactobacillus fermentum (referred to as biogenic silver or bio-Ag⁰) has been reported to exhibit antiviral properties. The microscale bacterial carrier matrix serves as a scaffold for Ag⁰ particles, preventing aggregation during encapsulation. In this study, bio-Ag⁰ was immobilized in different microporous PVDF membranes using two different pre-treatments of bio-Ag⁰ and the immersion-precipitation method. Inactivation of UZ1 bacteriophages using these membranes was successfully demonstrated and was most probably related to the slow release of Ag⁺ from the membranes. At least a 3.4 log decrease of viruses was achieved by application of a membrane containing 2500 mg bio-Ag⁰_powder m⁻² in a submerged plate membrane reactor operated at a flux of 3.1 L m⁻² h⁻¹. Upon startup, the silver concentration in the effluent initially increased to 271 μg L⁻¹ but after filtration of 31 L m⁻², the concentration approached the drinking water limit ( = 100 μg L⁻¹). A virus decline of more than 3 log was achieved at a membrane flux of 75 L m⁻² h⁻¹, showing the potential of this membrane technology for water disinfection on small scale.     

Transformation of metals speciation in a combined landfill leachate treatment

Landfill leachate was treated by a combined sequential batch reactor (SBR), coagulation, Fenton oxidation and biological aerated filter (BAF) technology. The metals in treatment process were fractionated into three fractions: particulate and colloidal (size charge filtration), free ion/labile (cation exchange) and non-labile fractions. Fifty percent to 66% Cu, Ni, Zn, Mn, Pb and Cd were present as particulate/colloidal matter in raw leachate, whereas Cr was present 94.9% as non-labile complexes. The free ion/labile fractions of Ni, Zn, Mg, Mn, Pb and Cd increased significantly after treatment except Cr. Fifty-nine percent to 100% of Al was present mainly as particulate/colloidal matter > 0.45 μm and the remaining portions were predicted as non-labile complexes except in coagulation effluent. The speciation of Fe varied significantly in various individual processes. Visual MINTEQ simulation showed that 95-100% colloidal species for Cu, Cd and Pb were present as metal-humic complexes even with the lower dissolved organic carbon. Optimum agreements for the free ion/labile species were within acidic solution, whereas under-estimated in alkaline effluents. Overestimated particulate/colloidal fraction consisted with the hypothesis that a portion of colloids in fraction < 0.45 μm were considered as dissolved.     

Impacts of pollution derived from ship wrecks on the marine environment on the basis of s/s “Stuttgart” (Polish coast, Europe)

In 1943 the German hospital ship s/s Stuttgart (Lazaretschiff “C”) was sunk close to the port of Gdynia (Gulf of Gdańsk — Polish coast). This and other actions (undertaken after the war to remove the wreck) led to pollution of the sea bottom with oil derivatives.During our studies (2009) 11 surface sediment and water samples were collected as well as sediment core samples at 4 locations in order to determine the concentration levels of priority pollutants belonging to polycyclic aromatic hydrocarbons (PAH) and polychlorinated biphenyls (PCB). The concentrations of 16 PAH and 7 PCB were analysed with GC-MS. ΣPAH varied between 11.54 ± 0.39 and 206.7 ± 6.5 mg/kg dry weight in the surface sediments, and from 0.686 ± 0.026 to 1291 ± 53 mg/kg dry weight in the core samples. Contamination in the core samples collected may reach a depth of at least 230-240 cm (deepest sample studied). The PAH-group profiles in all surface sediment samples suggest a pyrolytic source of PAH, while the results obtained for core samples indicate a mixed pattern of pyrolytic and petrogenic inputs of PAH. Results obtained may suggest also that fuel residues being present at sea bottom is not crude oil derived but results from coal processing (synthetic fuel). The sum of PCB in surface sediments ranged from 0.761 ± 0.068 to 6.82 ± 0.28 μg/kg dry weight (except for sampling point W2, where ΣPCB was 108.8 ± 4.4 μg/kg dry weight). The strong correlation between PAH and PCB levels, and the fact that PCB are present only in the surface sediments, suggest that the compounds in these sediments got there as a result of emission from urban areas, entering the aquatic environment via atmospheric deposition. PCB levels in the sediment core samples were generally very low and in most cases did not exceed the method quantification limit.     

Stepwise effects of the BCR sequential chemical extraction procedure on dissolution and metal release from common ferromagnesian clay minerals: a combined solution chemistry and X-ray powder diffraction study

Sequential extraction procedures (SEPs) are commonly used to determine speciation of trace metals in soils and sediments. However, the non-selectivity of reagents for targeted phases has remained a lingering concern. Furthermore, potentially reactive phases such as phyllosilicate clay minerals often contain trace metals in structural sites, and their reactivity has not been quantified. Accordingly, the objective of this study is to analyze the behavior of trace metal-bearing clay minerals exposed to the revised BCR 3-step plus aqua regia SEP. Mineral quantification based on stoichiometric analysis and quantitative powder X-ray diffraction (XRD) documents progressive dissolution of chlorite (CCa-2 ripidolite) and two varieties of smectite (SapCa-2 saponite and SWa-1 nontronite) during steps 1-3 of the BCR procedure. In total, 8 (± 1) % of ripidolite, 19 (± 1) % of saponite, and 19 (± 3) % of nontronite (% mineral mass) dissolved during extractions assumed by many researchers to release trace metals from exchange sites, carbonates, hydroxides, sulfides and organic matter. For all three reference clays, release of Ni into solution is correlated with clay dissolution. Hydrolysis of relatively weak Mg-O bonds (362 kJ/mol) during all stages, reduction of Fe(III) during hydroxylamine hydrochloride extraction and oxidation of Fe(II) during hydrogen peroxide extraction are the main reasons for clay mineral dissolution. These findings underscore the need for precise mineral quantification when using SEPs to understand the origin/partitioning of trace metals with solid phases.