Treatment of naphthalene-2-sulfonic acid from tannery wastewater by a granular activated carbon fixed bed inoculated with bacterial isolates Arthrobacter globiformis and Comamonas testosteroni

The kinetics of naphthalene-2-sulfonic acid (2-NSA) adsorption by granular activated carbon (GAC) were measured and the relationships between adsorption, desorption, bioavailability and biodegradation assessed. The conventional Langmuir model fitted the experimental sorption isotherm data and introduced 2-NSA degrading bacteria, established on the surface of the GAC, did not interfere with adsorption. The potential value of GAC as a microbial support in the aerobic degradation of 2-NSA by Arthrobacter globiformis and Comamonas testosteroni was investigated. Using both virgin and microbially colonised GAC, adsorption removed 2-NSA from the liquid phase up to its saturation capacity of 140 mg/g GAC within 48 h. However, between 83.2% and 93.3% of the adsorbed 2-NSA was bioavailable to both bacterial species as a source of carbon for growth. In comparison to the non-inoculated GAC, the combination of rapid adsorption and biodegradation increased the amount (by 70–93%) of 2-NSA removal from the influent phase as well as the bed-life of the GAC (from 40 to >120 d). A microbially conditioned GAC fixed-bed reactor containing 15 g GAC removed 100% 2-NSA (100 mg/l) from tannery wastewater at an empty bed contact time of 22 min for a minimum of 120 d without the need for GAC reconditioning or replacement. This suggests that small volume GAC bioreactors could be used for tannery wastewater recycling.

Hydraulic performance of geosynthetic clay liners to sulfuric acid solutions

The ability of geosynthetic clay liners (GCLs) to contain acidic mining leachates is examined. The results of saturated hydraulic conductivity (k) of two GCLs permeated with sulfuric acid solutions (H2SO4) at 0.015M, 0.125M and 0.5M concentrations are reported. Also, the saturated k values of consolidated (35kPa) bentonite cakes made from sodium bentonite extracted from both GCLs were compared to a commonly used magnesium-sodium form bentonite. Chemical compatibility and effects of pre-hydration and effective stress were assessed as part of this study. Results indicated that an increased acid concentration (ionic strength) increased the k of all tested specimens. The ratio of the k0.5 values for non-prehydrated specimens permeated with 0.5M H2SO4 to the kw values for specimens permeated with deionized (DI) water (k0.5/kw) ranged from 10 to 110. Pre-hydration (50-140% water content) and increased effective stress (35-200kPa) improved the performance of GCLs (lower k). Strong correlations were observed between k and liquid limit and swell index parameters independent of pre-hydration and effective stress in this study. However, care should still be taken when using these correlations to evaluate hydraulic performance because the intrinsic micro-structure properties of bentonite, such as porosity, should also be considered. This work showed that, for example, high SI of bentonite does not translate necessarily to a better hydraulic performance of GCLs.

Acid induced degradation of the bentonite component used in geosynthetic clay liners

Bentonite is a natural clay mineral widely used in the mining and solid waste containment industry, for example, as a soil mixture for the construction of seepage barriers, or as a component of geosynthetic clay liners (GCLs), to provide low hydraulic conductivity. However, degradation of bentonites generally occurs when permeated with acid solutions, such as encountered in mining applications, which may influence physical properties, and particularly, the hydraulic performance of geosynthetic clay liners.In this paper, properties such as Atterberg limits, free swell index, and fluid loss of three bentonites were measured with different concentrations of sulphuric acid solutions. These properties were found to deteriorate even with low (0.015 M) sulphuric acid solutions; higher concentrations (up to 1 M) resulted in larger degradation. X-ray diffraction and infrared spectroscopy were used to monitor the change of bentonites after interaction with the acid solutions. Acid leachates in general result in the overall degradation of the hydraulic performance of geosynthetic clay liners and potentially, any bentonite-soil mixture.

Inhibition of myeloperoxidase-mediated hypochlorous acid production by nitroxides

Tissue damage resulting from the extracellular production of HOCl (hypochlorous acid) by the MPO (myeloperoxidase)-hydrogen peroxide-chloride system of activated phagocytes is implicated as a key event in the progression of a number of human inflammatory diseases. Consequently, there is considerable interest in the development of therapeutically useful MPO inhibitors. Nitroxides are well established antioxidant compounds of low toxicity that can attenuate oxidative damage in animal models of inflammatory disease. They are believed to exert protective effects principally by acting as superoxide dismutase mimetics or radical scavengers. However, we show here that nitroxides can also potently inhibit MPO-mediated HOCl production, with the nitroxide 4-aminoTEMPO inhibiting HOCl production by MPO and by neutrophils with IC50 values of approx. 1 and 6 μM respectively. Structure–activity relationships were determined for a range of aliphatic and aromatic nitroxides, and inhibition of oxidative damage to two biologically-important protein targets (albumin and perlecan) are demonstrated. Inhibition was shown to involve one-electron oxidation of the nitroxides by the compound I form of MPO and accumulation of compound II. Haem destruction was also observed with some nitroxides. Inhibition of neutrophil HOCl production by nitroxides was antagonized by neutrophil-derived superoxide, with this attributed to superoxide-mediated reduction of compound II. This effect was marginal with 4-aminoTEMPO, probably due to the efficient superoxide dismutase-mimetic activity of this nitroxide. Overall, these data indicate that nitroxides have considerable promise as therapeutic agents for the inhibition of MPO-mediated damage in inflammatory diseases.

Effect of thermal treatment on adsorption-desorption of ammonia and sulfur dioxide on palygorskite : change of surface acid-alkali properties

Thermally activated Palygorskite (Pg) has been found to be a good adsorbent material for ammonia (NH3) and sulfur dioxide (SO2). This research investigated the effect of thermal treatment on pore structure and surface acid-alkali properties of Pg through the adsorption-desorption of NH3 and SO2. The results showed that, up to 200 °C, the adsorption of NH3 on Pg was significantly higher than SO2. This was due to NH3 being adsorbed in the internal surface of Pg and forming hydrogen bonds (H-bonds) with coordinated water. The increase in thermal treatment temp. from 150 to 550 °C, showed a gradual decrease in the no. of surface acid sites, while the no. of surface alk. sites increased from 200 to 400 °C. The change of surface acidity-alk. sites is due to the collapse of internal channels of Pg and desorption of different types of hydroxyls assocd. with the Pg structure.

Combination of MEK-ERK inhibitor and hyaluronic acid has a synergistic effect on anti-hypertrophic and pro-chondrogenic activities in osteoarthritis treatment

We hypothesised that a potentially disease-modifying osteoarthritis (OA) drug such as hyaluronic acid (HA) given in combination with anti-inflammatory signalling agents such as mitogen-activated protein kinase kinase–extracellular signal-regulated kinase (MEK-ERK) signalling inhibitor (U0126) could result in additive or synergistic effects on preventing the degeneration of articular cartilage. Chondrocyte differentiation and hypertrophy were evaluated using human OA primary cells treated with either HA or U0126, or the combination of HA + U0126. Cartilage degeneration in menisectomy (MSX) induced rat OA model was investigated by intra-articular delivery of either HA or U0126, or the combination of HA + U0126. Histology, immunostaining, RT-qPCR, Western blotting and zymography were performed to assess the expression of cartilage matrix proteins and hypertrophic markers. Phosphorylated ERK (pERK)1/2-positive chondrocytes were significantly higher in OA samples compared with those in healthy control suggesting the pathological role of that pathway in OA. It was noted that HA + U0126 significantly reduced the levels of pERK, chondrocyte hypertrophic markers (COL10 and RUNX2) and degenerative markers (ADAMTs5 and MMP-13), however, increased the levels of chondrogenic markers (COL2) compared to untreated or the application of HA or U0126 alone. In agreement with the results in vitro, intra-articular delivery of HA + U0126 showed significant therapeutic improvement of cartilage in rat MSX OA model compared with untreated or the application of HA or U0126 alone. Our study suggests that the combination of HA and MEK-ERK inhibition has a synergistic effect on preventing cartilage degeneration.

Natural improvements of geochemical conditions of acid sulfate soils caused by free tidal inundation and its effects on the mangrove seedlings

Acid sulfate soils (ASS) are one of the stressor factors that cause many mangrove restoration projects to fail. Achieving successful rehabilitation in an ASS affected area requires an understanding of the geochemical conditions that influence the establishment and growth of mangrove seedlings. This study evaluated the effect of tidal inundation on geochemical conditions on sub layer to better understand their impacts on the density, establishment, and growth of mangrove seedlings. This study also examined the geochemical conditions under which mangrove seedlings can establish naturally, and/or be replanted in abandoned aquaculture ponds. The study area was in an area of abandoned aquaculture ponds situated in the Mare District, adjacent to Bone Bay, South Sulawesi, Indonesia.The pH, pHfox, redox potential, organic content, water soluble sulfate, SKCl, SPOS, and grain size of the soil from the sediment core at + 10 - 15 cm depth near roots were measured using. Pyrite analysis were conducted for the top and sub sediments. The density, establishment, and the relative root growth of Rhizophoraceae were also determined. Free tidal inundation at abandoned pond sites improved the sediment quality. The high density, establishment, and growth of mangrove seedlings were characterized by freely drained areas with a higher pH (field and oxidisable), lower organic content, and high proportion of silt/clay. Higher density and growth also correlated to reduced environments. Sulfur species did not influence the density, establishment, and growth of the seedlings directly. The supply of propagules from the mangrove stands, or access from good waterways were also important for seedlings to establish naturally.

Properties of hand-made clay balls used as a novel filter media

Filtration using granular media such as quarried sand, anthracite and granular activated carbon is a well-known technique used in both water and wastewater treatment. A relatively new prefiltration method called pebble matrix filtration (PMF) technology has been proved effective in treating high turbidity water during heavy rain periods that occur in many parts of the world. Sand and pebbles are the principal filter media used in PMF laboratory and pilot field trials conducted in the UK, Papua New Guinea and Serbia. However during first full-scale trials at a water treatment plant in Sri Lanka in 2008, problems were encountered in sourcing the required uniform size and shape of pebbles due to cost, scarcity and Government regulations on pebble dredging. As an alternative to pebbles, hand-made clay pebbles (balls) were fired in a kiln and their performance evaluated for the sustainability of the PMF system. These clay balls within a filter bed are subjected to stresses due to self-weight and overburden, therefore, it is important that clay balls should be able to withstand these stresses in water saturated conditions. In this paper, experimentally determined physical properties including compression failure load (Uniaxial Compressive Strength) and tensile strength at failure (theoretical) of hand-made clay balls are described. Hand-made clay balls fired between the kiln temperatures of 875oC to 960oC gave failure loads of between 3.0 kN and 7.1 kN. In another test when clay balls were fired to 1250oC the failure load was 35.0 kN compared to natural Scottish cobbles with an average failure load of 29.5 kN. The uniaxial compressive strength of clay balls obtained by experiment has been presented in terms of the tensile yield stress of clay balls. Based on the effective stress principle in soil mechanics, a method for the estimation of maximum theoretical load on clay balls used as filter media is proposed and compared with experimental failure loads.

Rapid differentiation of isomeric lipids by photodissociation mass spectrometry of fatty acid derivatives

RATIONALE Both traditional electron ionization and electrospray ionization tandem mass spectrometry have demonstrated limitations in the unambiguous identification of fatty acids. In the former case, high electron energies lead to extensive dissociation of the radical cations from which little specific structural information can be obtained. In the latter, conventional collision-induced dissociation (CID) of even-electron ions provides little intra-chain fragmentation and thus few structural diagnostics. New approaches that harness the desirable features of both methods, namely radical-driven dissociation with discrete energy deposition, are thus required. METHODS Herein we describe the derivatization of a structurally diverse suite of fatty acids as 4-iodobenzyl esters (FAIBE). Electrospray ionization of these derivatives in the presence of sodium acetate yields abundant [M+Na]+ ions that can be mass-selected and subjected to laser irradiation (=266nm) on a modified linear ion-trap mass spectrometer. RESULTS Photodissociation (PD) of the FAIBE derivatives yields abundant radical cations by loss of atomic iodine and in several cases selective dissociation of activated carboncarbon bonds (e.g., at allylic positions) are also observed. Subsequent CID of the [M+NaI]center dot+ radical cations yields radical-directed dissociation (RDD) mass spectra that reveal extensive carboncarbon bond dissociation without scrambling of molecular information. CONCLUSIONS Both PD and RDD spectra obtained from derivatized fatty acids provide a wealth of structural information including the position(s) of unsaturation, chain-branching and hydroxylation. The structural information obtained by this approach, in particular the ability to rapidly differentiate isomeric lipids, represents a useful addition to the lipidomics tool box. Copyright (c) 2013 John Wiley & Sons, Ltd.

Handmade clay balls and recycled crush glass as alternative media in water filtration

For many years materials such as quarried sand, anthracite, and granular activated carbon have been the principal media-products traditionally used in water and wastewater filtration plants. Pebble Matrix Filtration (PMF) is a novel non-chemical, sustainable pre-treatment method of protecting Slow Sand Filters (SSF) from high turbidity during heavy monsoon periods. PMF uses sand and pebbles as the filter media and the sustainability of this new technology might depend on availability and supply of pebbles and sand, both finite resources. In many countries there are two principal methods of obtaining pebbles and sand, namely dredging from rivers and beaches, and due to the scarcity of these resources in some countries the cost of pebbles is often 4-5 times higher than that of sand. In search for an alternative medium to pebbles after some preliminary laboratory tests conducted in Colombo-Sri Lanka, Poznan-Poland and Cambridge-UK, a 100-year-old brick factory near Sudbury, Suffolk, has produced hand-made clay pebbles satisfying the PMF quality requirements. As an alternative to sand, crushed recycled glass from a UK supplier was used and the PMF system was operated together with hand-made clay balls in the laboratory for high turbidity removal effectively. The results of laboratory experiments with alternative media are presented in this paper. There are potential opportunities for recycled crushed glass and clay ball manufacturing processes in some countries where they can be used as filter media.

The loss of carbon dioxide from activated perbenzoate anions in the gas phase : Unimolecular rearrangement via epoxidation of the benzene ring

The unimolecular reactivities of a range of perbenzoate anions (X-C6H5CO3-), including the perbenzoate anion itself (X=H), nitroperbenzoates (X=para-, meta-, ortho-NO2), and methoxyperbenzoates (X=para-, meta-OCH3) were investigated in the gas phase by electrospray ionization tandem mass spectrometry. The collision-induced dissociation mass spectra of these compounds reveal product ions consistent with a major loss of carbon dioxide requiring unimolecular rearrangement of the perbenzoate anion prior to fragmentation. Isotopic labeling of the perbenzoate anion supports rearrangement via an initial nucleophilic aromatic substitution at the ortho carbon of the benzene ring, while data from substituted perbenzoates indicate that nucleophilic attack at the ipso carbon can be induced in the presence of electron-withdrawing moieties at the ortho and para positions. Electronic structure calculations carried out at the B3LYP/6311++G(d,p) level of theory reveal two competing reaction pathways for decarboxylation of perbenzoate anions via initial nucleophilic substitution at the ortho and ipso positions, respectively. Somewhat surprisingly, however, the computational data indicate that the reaction proceeds in both instances via epoxidation of the benzene ring with decarboxylation resulting-at least initially-in the formation of oxepin or benzene oxide anions rather than the energetically favored phenoxide anion. As such, this novel rearrangement of perbenzoate anions provides an intriguing new pathway for epoxidation of the usually inert benzene ring.

Molecular and clinical characteristics of tricarboxylic acid cycle-associated tumors

Hereditary leiomyomatosis and renal cell cancer (HLRCC) is a rare, dominantly inherited tumor predisposition syndrome characterized by benign cutaneous and uterine (ULM) leiomyomas, and sometimes renal cell cancer (RCC). A few cases of uterine leiomyosarcoma (ULMS) have also been reported. Mutations in a nuclear gene encoding fumarate hydratase (FH), an enzyme of the mitochondrial tricarboxylic acid cycle (TCA cycle), underlie HLRCC. As a recessive condition, germline mutations in FH predispose to a neurological defect, FH deficiency (FHD). Hereditary paragangliomatosis (HPGL) is a dominant disorder associated with paragangliomas and pheochromocytomas. Inherited mutations in three genes encoding subunits of succinate dehydrogenase (SDH), also a TCA cycle enzyme, predispose to HPGL. Both FH and SDH seem to act as tumor suppressors. One of the consequences of the TCA cycle defect is abnormal activation of HIF1 pathway ( pseudohypoxia ) in the HLRCC and HPGL tumors. HIF1 drives transcription of genes encoding e.g. angiogenetic factors which can facilitate tumor growth. Recently hypoxia/HIF1 has been suggested to be one of the causes of genetic instability as well. One of the aims of this study was to broaden the clinical definers of HLRCC. To determine the cancer risk and to identify possible novel tumor types associated with FH mutations eight Finnish HLRCC/FHD families were extensively evaluated. The extension of the pedigrees and the Finnish Cancer Registry based tumor search yielded genealogical and cancer data of altogether 868 individuals. The standardized incidence ratio-based comparison of HLRCC/FHD family members with general Finnish population revealed 6.5-fold risk for RCC. Moreover, risk for ULMS was highly increased. However, according to the recent and more stringent diagnosis criteria of ULMS many of the HLRCC uterine tumors previously considered malignant are at present diagnosed as atypical or proliferative ULMs (with a low risk of recurrence). Thus, the formation of ULMS (as presently defined) in HLRCC appears to be uncommon. Though increased incidence was not observed, interestingly the genetic analyses suggested possible association of breast and bladder cancer with loss of FH. Moreover, cancer cases were exceptionally detected in an FHD family. Another clinical finding was the conventional (clear cell) type RCC of a young Spanish HLRCC patient. Conventional RCC is distinct from the types previously observed in this syndrome but according to these results, FH mutation may underlie some of young conventional cancer cases. Secondly, the molecular pathway from defective TCA cycle to tumor formation was intended to clarify. Since HLRCC and HPGL tumors display abnormally activated HIF1, the hypothesis on the link between HIF1/hypoxia and genetic instability was of interest to study in HLRCC and HPGL tumor material. HIF1α (a subunit of HIF1) stabilization was confirmed in the majority of the specimens. However, no repression of MSH2, a protein of DNA mismatch repair system, or microsatellite instability (MSI), an indicator of genetic instability, was observed. Accordingly, increased instability seems not to play a role in the tumorigenesis of pseudohypoxic TCA cycle-deficient tumors. Additionally, to study the putative alternative functions of FH, a recently identified alternative FH transcript (FHv) was characterized. FHv was found to contain instead of exon 1, an alternative exon 1b. Differential subcellular distribution, lack of FH enzyme activity, low mRNA expression compared to FH, and induction by cellular stress suggest FHv to have a role distinct from FH, for example in apoptosis or survival. However, the physiological significance of FHv requires further elucidation.

Lactic acid bacteria and their antimicrobial peptides : Induction,detection,partial characterization, and potential applications

Bacteriocin-producing lactic acid bacteria and their isolated peptide bacteriocins are of value to control pathogens and spoiling microorganisms in foods and feed. Nisin is the only bacteriocin that is commonly accepted as a food preservative and has a broad spectrum of activity against Gram-positive organisms including spore forming bacteria. In this study nisin induction was studied from two perspectives, induction from inside of the cell and selection of nisin inducible strains with increased nisin induction sensitivity. The results showed that a mutation in the nisin precursor transporter NisT rendered L. lactis incapable of nisin secretion and lead to nisin accumulation inside the cells. Intracellular proteolytic activity could cleave the N-terminal leader peptide of nisin precursor, resulting in active nisin in the cells. Using a nisin sensitive GFP bioassay it could be shown, that the active intracellular nisin could function as an inducer without any detectable release from the cells. The results suggested that nisin can be inserted into the cytoplasmic membrane from inside the cell and activate NisK. This model of two-component regulation may be a general mechanism of how amphiphilic signals activate the histidine kinase sensor and would represent a novel way for a signal transduction pathway to recognize its signal. In addition, nisin induction was studied through the isolation of natural mutants of the GFPuv nisin bioassay strain L. lactis LAC275 using fl uorescence-activated cell sorting (FACS). The isolated mutant strains represent second generation of GFPuv bioassay strains which can allow the detection of nisin at lower levels. The applied aspect of this thesis was focused on the potential of bacteriocins in chicken farming. One aim was to study nisin as a potential growth promoter in chicken feed. Therefore, the lactic acid bacteria of chicken crop and the nisin sensitivity of the isolated strains were tested. It was found that in the crop Lactobacillus reuteri, L. salivarius and L. crispatus were the dominating bacteria and variation in nisin resistance level of these strains was found. This suggested that nisin may be used as growth promoter without wiping out the dominating bacterial species in the crop. As the isolated lactobacilli may serve as bacteria promoting chicken health or reducing zoonoosis and bacteriocin production is one property associated with probiotics, the isolated strains were screened for bacteriocin activity against the pathogen Campylobacter jejuni. The results showed that many of the isolated L. salivarius strains could inhibit the growth of C. jejuni. The bacteriocin of the L. salivarius LAB47 strain, with the strongest activity, was further characterized. Salivaricin 47 is heat-stable and active in pH range 3 to 8, and the molecular mass was estimated to be approximately 3.2 kDa based on tricine SDS-PAGE analysis.