In situ remediation of arsenic in simulated groundwater using zerovalent iron: laboratory column tests on combined effects of phosphate and silicate

We performed three column tests to study the behavior of permeable reactive barrier (PRB) materials to remove arsenic under dynamic flow conditions in the absence as well as in the presence of added phosphate and silicate. The column consisted of a 10.3 cm depth of 50:50 (w:w, Peerless iron:sand) in the middle and a 10.3 cm depth of a sediment from Elizabeth City, NC, in both upper and lower portions of the 31-cm-long glass column (2.5 cm in diameter) with three side sampling ports. The flow velocity (upflow mode) was maintained at 4.3 m d(-1) during the 3-4-month experiments. As expected, dissolved As concentrations in different positions of the column generally followed the order: column influent > bottom port effluent > middle port effluent > top port effluent > column effluent. The steady-state As removal in the middle Peerless iron and sand mixture zone might be attributed to the continuous supply of corroded iron in the form of iron oxides and hydroxides that served as the sorbents for both As(V) and As(III). Consistent with previous batch study findings, dissolved phosphate (0.5 or 1 mg of P L(-1)) and silicate (10 or 20 mg of Si L(-1)) showed strong inhibition for As(V) and As(III) (1 mg of As(V) L(-1) + 1 mg of As(III) L(-1) in 7 mM NaCl + 0.86 mM CaSO4) removal by Peerless iron in the column tests. The presence of combined phosphate and silicate resulted in earlier breakthrough (C = 0.5C0) and earlier complete breakthrough of dissolved arsenic relative to absence of added phosphate and silicate in the bottom port effluent. Competition between As(V)/As(III) and phosphate/silicate forthe sorption sites on the corrosion products of Peerless iron seems to be the cause of the observations. This effect is especially important in the case of silicate for designing a PRB of zerovalent iron for field use because dissolved silicate is ubiquitous in terrestrial waters.     

Aqueous solubility diagrams for cementitious waste stabilization systems. 3. Mechanism of zinc immobilizaton by calcium silicate hydrate

Zinc oxide was added during hydration of alite (C3S) as an analogue for solidification/stabilization by cement of metal-bearing hazardous waste. Curing of samples was stopped at various intervals between 8 h and 100 d, and the reaction products were analyzed by both X-ray diffraction (XRD) and X-ray absorption spectroscopy (EXAFS at Zn, Ca, and Si K-edges). Calcium zincate hydrate (CaZn2(OH)6 x 2H2O) initially formed together with calcium silicate hydrate (CSH) vanishes from X-ray diffractograms after 14 d, and no other crystalline Zn-bearing phase could be detected thereafter. EXAFS Zn K-edge data analysis reveals that Zn(O,OH)4 tetrahedra continue to determine the first shell coordination. However, a new Zn-Si bond appears in the second coordination shell as indicated by both Zn K-edge and Si K-edge EXAFS. Together with the Ca-Zn and Ca-Ca shells derived from the Ca K-edge EXAFS spectra, a structural model for the site occupation of Zn in CSH is proposed, whereby the Zn(O,OH)4 tetrahedra are bound in layer rather than interlayer positions substituting for the silicate bridging tetrahedra and/or at terminal silicate chain sites. This structural model enables ultimately the formulation of a thermodyamic Lippmann model to predict the aqueous solubility of Zn in solid solution with a CSH phase of a Ca/Si ratio fixed to unity.     

Sorption of selected endocrine disrupting chemicals to different aquatic colloids

The sorption of seven endocrine disrupting chemicals (EDCs) to aquatic colloids was determined by cross-flow ultrafiltration (CFUF) followed by gas chromatography-mass spectrometry (GC-MS). Results show that the colloidal organic carbon normalized sorption coefficient (Kcoc) of EDCs to different aquatic colloids varies by a factor of 6-12 because such colloids are of different origin. Through characterization of colloidal samples, a significant relationship was established between Kcoc values and the molar extinction coefficient of colloids at 280 nm, whereas no other colloidal properties such as elemental ratios were correlated with Kcoc values. The results are consistent with other reports of the importance of the quality of sorbents such as their aromatic carbon content in sorbing various organic pollutants. The presence of a surfactant was found to increase Kcoc values for estrone (El) and 17alpha-ethynylestradiol (EE2). The method was subsequently applied for determining EDC concentrations in field samples, where both conventional and truly dissolved EDCs showed higher concentrations close to sewage outfalls than either upstream or downstream, confirming the sourceconcentration relationship. In addition, the truly dissolved EDC concentrations were lower than the conventional dissolved concentrations, confirming that there were interactions between aquatic colloids and EDCs. It is estimated that between 10 and 29% of EDCs are associated with aquatic colloids. As colloids are highly abundant in rivers and ocean, they will therefore play a significant role in the environmental behavior and fate of EDCs.     

Aqueous solubility diagrams for cementitious waste stabilization systems. 4. A carbonation model for Zn-doped calcium silicate hydrate by Gibbs energy minimization

A thermodynamic Gibbs energy minimization (GEM) solid solution-aqueous solution (SSAS) equilibrium model was used to determine the solubility of Zn from calcium silicate hydrate (CSH) phases doped with 0, 0.1, 1, 5, and 10% Zn at a unity (Ca+Zn)/Si molar ratio. Both the stoichiometry and standard molar Gibbs energy (G(o)298) of the Zn-bearing end-member in the ideal ternary Zn-bearing calcium silicate hydrate (CZSH) solid solution were determined by a "dual-thermodynamic" (GEM-DT) estimation technique. The SSAS model reproduces a complex sequence of reactions suggested to occur in a long-term weathering scenario of cementitious waste forms at subsurface repository conditions. The GEM model of CZSH leaching at several Zn loadings and solid/water (s/w) ratios in a C02-free system showed that, upon complete dissolution of portlandite and calcium zincate phases at decreasing s/w < 0.01 mol x kg(H2O)(-1), the total dissolved concentrations Si(aq), Ca(aq), and Zn(aq) are controlled by a CZSH solid solution of changing composition, with a trough-like Znaq drop by 2-3 orders of magnitude. Carbonation was simulated in another GEM model run series by CO2 titration of the system with initial s/w approximately 0.9 mol/kg(H2O). Formation of (Ca,Zn)-CO3 nonideal solid solution was predicted already at early reaction stage in the presence of both portlandite and calcium zincate hydrate phases. Upon their disappearance, pH, Zn(aq), C(aq), and fCO2 were predicted to change due to the incongruent dissolution of two concurrent CZSH-I and CZSH-II solid solutions, until the total re-partitioning of Ca and Zn into a carbonate solid solution coexisting with amorphous silica at fCO2 > 0.1 bar. Along this solid-phase transition, dissolved Zn(aq) concentrations follow a highly nonlinear trend. The model results predict that at low to moderate Zn loading (< or = 1% per mole Si), CZSH-type compounds can efficiently immobilize Zn in the near field of a cement-stabilized waste repository.     

聚合硅酸硫酸铝铁处理造纸中段废水

该文采用硫酸铝、硫酸铁和硅酸钠等为原料,制备聚合硅酸硫酸铝铁（polymeric aluminum ferric sulfate,PAFSS）絮凝剂,研究了n（Si）：n（Al）：n（Fe）、pH等因素对所制PAFSS在去除造纸废水的色度及COD_（Cr）时的影响,对PAFSS的物化特性进行了系统的研究。结果表明：n（Si）：n（Al）：n（Fe）、pH和反应温度对PAFSS性能有重要影响;聚硅酸与铝离子、铁离子及铝铁水解产物间存在一定的络合作用,这种作用对PAFSS聚集体的结构形貌、铝离子和铁离子的水解聚合过程及铝、铁水解产物的形态分布都有一定的影响。在n（Fe＋Al）：n（Si）=3：1、n（Al）：n（Fe）=4：1、pH=4和温度为40℃等条件下制得的PAFSS对废水色度和COD_（Cr）有很好的去除效果,并通过对PAFSS絮凝机理分析,可知PAFSS的絮凝作用主要是通过电中和和吸附架桥2方面实现的。     

Dark oxidation of dissolved and liquid elemental mercury in aquatic environments

Elemental mercury (Hg0) can be found in liquid or dissolved forms in aquatic systems. Whereas dissolved Hg0 is measured in virtually all aquatic systems, liquid Hg0 droplets are mainly observed at poorly lit sediment/water interfaces of ecosystems with local point sources such as hydro-thermal vents, gold extraction sites, and near industrial facilities. Here, we report that, in the dark, liquid and dissolved forms of Hg behave differently with respect to their oxidation. Liquid Hg0 is rapidly oxidized in oxygenated solution in the presence of chloride. Liquid Hg0 oxidation rates are positively correlated with chloride concentrations and droplet surface area. When liquid Hg is removed from solution, the oxidation stops even though the solution is still saturated with dissolved Hg0. Liquid Hg0 droplets in oxygenated marine or brackish environments should be oxidized and release Hg2+ to solution. In freshwaters or anoxic seawater, liquid Hg will dissolve releasing Hg(aq)0 which, itself, will slowly oxidize.     

Uptake of Np(IV) by C-S-H phases and cement paste: an EXAFS study

Nuclear waste disposal concepts developed worldwide foresee the use of cementitious materials for the immobilization of long-lived intermediate level waste (ILW). This waste form may contain significant amounts of neptunium-237, which is expected to be present as Np(IV) under the reducing conditions encountered after the closure of the repository. Predicting the release of Np(IV) from the cementitious near field of an ILW repository requires a sufficiently detailed understanding of its interaction with the main sorbing components of hardened cement paste (HCP). In this study, the uptake of Np(IV) by calcium silicate hydrates (C-S-H) and HCP has been investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS studies on Np(IV)-doped C-S-H and HCP samples reveal that Np(IV) is predominantly incorporated in the structure of C-S-H phases having different Ca:Si ratios. The two main species identified correspond to Np(IV) in C-S-H with a Ca:Si mol ratio of 1.65 as in fresh cement and with a Ca:Si mol ratio of 0.75 as in highly degraded cement. The local structure of Np(IV) changes with the Ca:Si mol ratio and does not depend on pH. Furthermore, Np(IV) shows the same coordination environment in C-S-H and HCP samples. This study shows that C-S-H phases are responsible for the Np(IV) uptake by cementitious materials and further that incorporation in the interlayer of the C-S-H structure is the dominant uptake mechanism.     

Influence of biodegradation processes on the duration of CaCO3 as a pH buffer in municipal solid waste incinerator bottom ash

The long-term leachability of heavy metals from municipal solid waste incinerator (MSWI) bottom ash is of concern because of its potential use as a secondary construction material. Calcite is the most important long-term buffer in MSWI bottom ash as it buffers solutions during percolation and is an important factor in the control of heavy-metal mobility. It has been argued that biodegradation of residual organic material in the MSWI is a significant source of acidity. Model calculations have therefore been carried out to determine the influence of biodegradation on the longevity of the calcite buffer. Using the program STEADYQL, which couples thermodynamic equilibrium with kinetically controlled reactions, solution composition was estimated at steady state. The concentration of Ca dissolved from calcite was estimated in the presence and absence of gypsum as a function of the reaction rate of a number of slow reactions: aerobic, ferrogenic, sulfogenic, and methanogenic biodegradation; diffusion of O2 into the system; degassing of CO2 out of the system; and dissolution of Ca silicate. It was found that, independent of the rate, the biodegradation of organic matter had little influence on the longevity of the calcite buffer (between 2,000 and 3,000 yr for a deposit of 1 m in depth), that anaerobic biodegradation may have a slight retarding effect, and that calcite dissolution due to acid input via precipitation was negligible (around 3% of the total at reference conditions for rainwater with a pH value of 4.3).     

Starch gelatinization using sodium silicate: FTIR,DSC, XRPD,and NMR studies

The chemical and physical modifications of native maize starch subjected to treatment with aqueous Na silicate have been investigated. The application of FTIR, DSC, XRPD, and NMR analysis is discussed herein with respect to the interaction of Na silicate with starch in relation to gelatinization. XRPD results indicate that Na silicate, in the ionized form, disrupts the molecular structure of starch in a manner similar to thermally induced starch gelatinization. In addition, Na silicate forms new CO–O–SiO₂Na moieties with the amylopectin starch component. This was ascertained by the detection of the in‐plane vibration of the –Si–O as a distinctive FTIR band at 580–600 cm⁻¹ and the appearance of a new carboxyl group (–COOH) NMR chemical shift at 168 ppm for the amylopectin/Na silicate system. DSC analysis showed two adjacent endothermic transitions at 192 and 198°C for starch/amylopectin treated with Na silicate whereas amylose treated with Na silicate did not show any new endothermic/or exothermic transitions.     

Differences in dissolved cadmium and zinc uptake among stream insects: mechanistic explanations

This study examined the extent to which dissolved Cd and Zn uptake rates vary in several aquatic insect taxa commonly used as indicators of ecological health. We further attempted to explain the mechanisms underlying observed differences. By comparing dissolved Cd and Zn uptake rates in several aquatic insect species, we demonstrated that species vary widely in these processes. Dissolved uptake rates were not related to gross morphological features such as body size or gill size--features that influence water permeability and therefore have ionoregulatory importance. However, finer morphological features, specifically, the relative numbers of ionoregulatory cells (chloride cells), appeared to be related to dissolved metal uptake rates. This observation was supported by Michaelis-Menten type kinetics experiments, which showed that dissolved Cd uptake rates were driven by the numbers of Cd transporters and not by the affinities of those transporters to Cd. Calcium concentrations in exposure media similarly affected Cd and Zn uptake rates in the caddisfly Hydropsyche californica. Dissolved Cd and Zn uptake rates strongly co-varied among species, suggesting that these metals are transported by similar mechanisms.     

Linking cesium and strontium uptake to kaolinite weathering in simulated tank waste leachate

Weathering behavior of kaolinite was studied in batch systems under geochemical conditions characteristic of tank waste released to the vadose zone at the Hanford Site, WA (0.05 M Al(T), 2 M Na+, 1 M N03-, pH approximately 14, Cs+ and Sr2+ present as co-contaminants). Time series experiments were conducted from 0 to 369 d, with initial Cs+ and Sr2+ concentrations ranging from 10(-5) to 10(-3) M. Dissolution of kaolinite increased soluble Si and Al to maximum levels at 7 d (Cs and Sr concentrations of 10(-5) and 10(-4) M) or 33 d (Cs and Sr concentrations of 10(-3) M). Subsequent precipitation of Si and Al was coupled to the formation of oxalate-extractable solids that incorporated Cs and Sr. Strontium sorption was nearly complete within 24 h for initial Sr concentrations (Sr0) < or = 10(-4) whereas Cs uptake increased over the full year of the experiment for all initial Cs concentrations. Spectroscopic analyses revealed neoformed solids including the zeolite Na-Al silicate (Al-chabazite), and feldspathoids sodium aluminum nitrate silicate (NO3-sodalite), and sodium aluminum nitrate silicate hydrate (NO3-cancrinite), which can incorporate Cs. Single-pulse 27Al solid-state nuclear magnetic resonance (NMR) spectroscopyyielded first-order rate constants (k)for mineral transformation that decreased from 3.5 x 10(-3) to 2 x 10(-3) d(-1) as Cs and Sr concentrations were increased from 10(-5) to 10(-3) M. Discrete strontium silicate solids were also observed. The incongruent dissolution of kaolinite promoted the sequestration of contaminants into increasingly recalcitrant solid phases over the 1-yr time period.     

Mechanism of europium retention by calcium silicate hydrates: an EXAFS study

The uptake of Eu by calcium silicate hydrate (C-S-H) phases as a function of Eu/sorbate ratio (from 37 to 450 micromol g(-1) C-S-H), C-S-H Ca/Si mole ratio (1.3, 1.0, and 0.7), and initial supersaturating conditions was probed by solution kinetics experiments and extended X-ray absorption fine structure (EXAFS) spectroscopy, to shed light on the retention mechanism of trivalent radionuclides under waste repository conditions. The rates of Eu (9.7 x 10(-10) M) uptake in C-S-H suspensions and in solutions at equilibrium with C-S-H were rapid. Uptake of more than 90% of dissolved Eu was generally observed within 15 min. Europium LIII-edge EXAFS spectra collected on samples of Eu sorbed on, or coprecipitated in, C-S-H differed from that of Eu(OH)3(s) expected to precipitate under the pH conditions of C-S-H waters, ruling out compelling precipitation of pure hydroxide phases. Fourier transforms for EXAFS spectra for Eu in sorption/coprecipitation samples displayed comparable features at distances typical of neighboring cationic shells, pointing to similar crystallochemical environments. Optimal spectral simulations were obtained by assuming the presence of Si, Si/Ca, and Ca cationic shells surrounding Eu at distances of 3.2, 3.7-3.8, and 3.8-3.9 A, respectively. The nearly continuous distribution of (Si, Ca) backscattering shells parallels the distribution in Ca-(Ca, Si) interatomic distances in structural models of C-S-H. Discernible effects of experimental parameters on the Eu local environment were observed by comparison of Fourier transforms, but could not be confirmed by EXAFS quantitative analysis. These results indicate that sorbed or coprecipitated Eu is located at Ca structural sites in a C-S-H-like environment. Kinetics and spectroscopic results are consistent with either Eu diffusion within C-S-H particles or precipitation of Eu with Ca and Si creating a C-S-H-like solid phase.     

Evaluation of specific ultraviolet absorbance as an indicator of the chemical composition and reactivity of dissolved organic carbon

Specific UV absorbance (SUVA) is defined as the UV absorbance of a water sample at a given wavelength normalized for dissolved organic carbon (DOC) concentration. Our data indicate that SUVA, determined at 254 nm, is strongly correlated with percent aromaticity as determined by 13C NMR for 13 organic matter isolates obtained from a variety of aquatic environments. SUVA, therefore, is shown to be a useful parameter for estimating the dissolved aromatic carbon content in aquatic systems. Experiments involving the reactivity of DOC with chlorine and tetramethylammonium hydroxide (TMAH), however, show a wide range of reactivity for samples with similar SUVA values. These results indicate that, while SUVA measurements are good predictors of general chemical characteristics of DOC, they do not provide information about reactivity of DOC derived from different types of source materials. Sample pH, nitrate, and iron were found to influence SUVA measurements.     

Arsenic removal from Bangladesh tube well water with filter columns containing zerovalent iron filings and sand

Arsenic removal is often challenging due to high As(III), phosphate, and silicate concentrations and low natural iron concentrations. Application of zerovalent iron is promising, as metallic iron is widely available. However, removal mechanisms remained unclear and currently used removal units with iron have not been tested systematically, partly due to their large size and long operation time. This study investigated smaller filter columns with 3-4 filters, each containing 2.5 g of iron filings and 100-150 g of sand. At a flow rate of 1 L/h, these columns were able to treat 75-90 L of well water with 440 microg/L As, 1.8 mg/L P, 4.7 mg/L Fe, 19 mg/L Si, and 6 mg/L dissolved organic carbon (DOC) to below 50 microg/L As(tot), without addition of an oxidant. As(III) was oxidized in parallel to oxidation of corrosion-released Fe(II) by dissolved oxygen and sorbed on the forming hydrous ferric oxides (HFO). The open filter columns prevented anoxic conditions. DOC did not appear to interfere with arsenic removal. Manganese was reduced after a slight initial increase from 0.3 mg/L to below 0.1 mg/L. About 100 mg of Fe(0)/L of water was required, 3-5 times less than that for larger units with sand and iron turnings.     

SX-865澄清剂在低度白酒中的澄清机理

SX-865澄清剂主要成分为天然无机俚型硅酸盐粘土,化学成分主要是Si和Mg;具有大的表面积和孔隙度、较好的电动电位、较好的膨胀性、较好的阳离子交换性能、良好的选择吸附性、良好的流变性、良好的催化性能。吸附机理为通过增加大层间距,提高吸附有机物质,加快过滤速度。     

Influence of dissolved organic carbon on methylmercury bioavailability across Minnesota stream ecosystems

Stream ecosystems are widely contaminated by mercury (Hg) via atmospheric transport and deposition in watersheds. Dissolved organic carbon (DOC) is well-known to be the dominant ligand for aqueous methylmercury (MeHg), the bioaccumulative form of Hg in aquatic food webs. However, it is less clear if and how the concentration and character (e.g., aromaticity) of DOC influences the availability of dissolved MeHg to stream food webs. In this work, we analyzed total-Hg and/or MeHg concentrations in water, seston, and macroinvertebrates (filter-feeding hydropsychid caddisflies), and other physiochemical properties in 30 streams along a south-north geographic gradient in eastern Minnesota that corresponds to substantial changes in dominant land cover (i.e., agriculture, urban, wetland, and forest). In general, MeHg concentrations in seston and hydropsychids were higher in watersheds with more forest and wetland coverage, and increased with dissolved MeHg concentration. However, we found that the efficiency of MeHg incorporation into the stream food webs (i.e., bioconcentration factors of MeHg in both seston and hydropsychids, BCF(MeHg) = solid MeHg ÷ dissolved MeHg) decreased significantly with DOC concentration and aromaticity, suggesting that MeHg bioavailability to the base of food webs was attenuated at higher levels of terrestrial DOC. Therefore, our findings suggest that there is a dual role of DOC on MeHg cycling in streams: terrestrial DOC acts as the primary carrier ligand of dissolved MeHg for transport into surface waters, yet this aromatic DOC also attenuates dissolved MeHg uptake by aquatic food webs. Thus, consideration of MeHg bioavailability and its environmental regulation could help improve predictive models of MeHg bioaccumulation in stream ecosystems.     

Acid rain effects on aluminum mobilization clarified by inclusion of strong organic acids

Assessments of acidic deposition effects on aquatic ecosystems have often been hindered by complications from naturally occurring organic acidity. Measurements of pH and ANCG, the most commonly used indicators of chemical effects, can be substantially influenced by the presence of organic acids. Relationships between pH and inorganic Al, which is toxic to many forms of aquatic biota, are also altered by organic acids. However, when inorganic Al concentrations are plotted against ANC (the sum of Ca2+, Mg2+, Na+, and K+, minus S042-, N03-, and Cl-), a distinct threshold for Al mobilization becomes apparent. If the concentration of strong organic anions is included as a negative component of ANC, the threshold occurs at an ANC value of approximately zero, the value expected from theoretical charge balance constraints. This adjusted ANC is termed the base-cation surplus. The threshold relationship between the base-cation surplus and Al was shown with data from approximately 200 streams in the Adirondack region of New York, during periods with low and high dissolved organic carbon concentrations, and for an additional stream from the Catskill region of New York. These results indicate that (1) strong organic anions can contribute to the mobilization of inorganic Al in combination with SO42- and N03-, and (2) the presence of inorganic Al in surface waters is an unambiguous indication of acidic deposition effects.     

Major structural components in freshwater dissolved organic matter

Dissolved organic matter (DOM) contains a complex array of chemical components that are intimately linked to many environmental processes, including the global carbon cycle, and the fate and transport of chemical pollutants. Despite its importance, fundamental aspects, such as the structural components in DOM remain elusive, due in part to the molecular complexity of the material. Here, we utilize multidimensional nuclear magnetic resonance spectroscopy to demonstrate the major structural components in Lake Ontario DOM. These include carboxyl-rich alicyclic molecules (CRAM), heteropolysaccharides, and aromatic compounds, which are consistent with components recently identified in marine dissolved organic matter. In addition, long-range proton-carbon correlations are obtained for DOM, which support the existence of material derived from linear terpenoids (MDLT). It is tentatively suggested that the bulk of freshwater dissolved organic matter is aliphatic in nature, with CRAM derived from cyclic terpenoids, and MDLT derived from linear terpenoids. This is in agreement with previous reports which indicate terpenoids as major precursors of DOM. At this time it is not clear in Lake Ontario whether these precursors are of terrestrial or aquatic origin or whether transformations proceed via biological and/ or photochemical processes.     

Effects of postharvest sodium silicate treatment on pink rot disease and oxidative stress-antioxidative system in muskmelon fruit

Sodium silicate (Si) at 100 mM was used as a postharvest treatment agent of induction resistance on muskmelon (Cucumis melon L. cv. Yindi) to investigate the mechanism of controlling pink rot disease, which caused by Trichothecium roseum. Si treatment significantly reduced (P < 0.05) the lesion diameter of melons inoculated with T. roseum during storage. Si treatment increased the content of superoxide (O₂^•−) and could be further raised by challenged with T. roseum inoculation. The content of hydroxyl radical (·OH) in inoculated fruit was also increased. Both malondialdehyde (MDA) and hydrogen peroxide (H₂O₂) were also accumulated with Si treatment and challenged inoculation. Si treatment maintained membrane integrity in non-inoculated fruit, as compared to untreated control. Si treatment and challenge inoculation significantly (P < 0.05) increased the activity of superoxide dismutase (SOD), glutathione reductase (GR), peroxidase (POD), and polyphenoloxidase (PPO), while markedly decreased the activity of catalase (CAT) and ascorbic peroxidase (APX). Si treatment and challenge inoculation also enhanced the content of ascorbic acid (ASA) and glutathione (GSH). These findings suggested that the effects of sodium silicate on postharvest disease in muskmelon fruit may be associated with the elicitation of antioxidant defense system in fruit.     

Nitrogen cycling in natural waters using in situ, reagentless UV spectrophotometry with simultaneous determination of nitrate and nitrite

Reliable, high temporal, and spatial resolution data is essential for enhancing our understanding of aquatic nitrogen biogeochemical cycling. This paper describes a novel UV spectrophotometric sensor (ProPS, TriOS GmbH, Oldenburg, Germany) for the real time, in situ, high resolution simultaneous mapping of nitrate/nitrite (linearity 0.01 - 6 mg N L(-1), RSD's NO3-N 4-10%, NO2-N 7-14%) in fresh and estuarine waters. Good agreement (t test at p = 0.05) was found with MOOS-1 certified reference material and with reference segmented flow analysis data. River Taw deployments identified a diurnal cycle for NO3-N (0.22-0.63 mg L(-1), RSD 3.9%) and for NO2-N (0.01-0.28 mg L(-1), RSD 12.4%) with the photo-oxidation of dissolved organic nitrogen a source of diurnal nitrate/nitrite, and a large cyclical amplitude (30-62% of mean nitrate/nitrite). In situ Tamar Estuary nitrate/nitrite concentrations, mapped through the salinity gradient, were strongly correlated with suspended particulate material and inversely correlated with dissolved oxygen and pH, indicating midestuarine, bacterially mediated nitrification/denitrification, with the raised estuarine nitrite also significantly correlated with particulate organic nitrogen. Such previously unquantified inputs have important implications for N loadings calculated from coarse scale sampling and laboratory analysis, pollution assessment, and our understanding of the biological rhythms of aquatic organisms.