A photochemical source of methyl chloride in saline waters

It is shown experimentallythatthe methoxy group in simple lignin-like molecules can be the source of the methyl group in CH3Cl produced by a photochemical reaction in an aqueous solution of chloride. Terrestrially derived colored dissolved organic matter (CDOM) in river water also yields CH3Cl through a photochemical process in a chloride solution. CDOM extracted from subsurface ocean waters showed some ability to enhance photochemical production of CH3Cl while CDOM from surface water showed no effect. Reactions of the kind described in this paper may be contributors to the marine source of methyl chloride and possibly other alkyl halides.     

Design and implementation of a continuous microwave heating system for ballast water treatment

A continuous microwave system to treat ballast water inoculated with different invasive species was designed and installed atthe Louisiana State University Agricultural Center. The effectiveness of the system to deliver the required heating loads to inactivate the organisms present was studied. The targeted organisms were microalgae (Nannochloropsis oculata), zooplankton at two different growth stages (newly hatched brine shrimp-Artemia nauplii and adult Artemia), and oyster larvae (Crassosstrea virginica). The system was tested at two different flow rates (1 and 2 liters per min) and power levels (2.5 and 4.5 kW). Temperature profiles indicate that, depending on the species present and the growth stage, the maximum temperature increase will vary from 11.8 to 64.9 degrees C. The continuous microwave heating system delivered uniform and near-instantaneous heating at the outlet proving its effectiveness. The power absorbed and power efficiency varied for the species present. More than 80% power utilization efficiency was obtained at all flow rate and microwave power combinations for microalgae, Artemia nauplii and adults. Test results indicated that microwave treatment can be an effective tool for ballast water treatment, and current high treatment costs notwithstanding, this technique can be added as supplemental technology to the palette of existing treatment methods.     

On the influence of natural mineral waters and fruit juices on the decay of ascorbic acid radicals in aqueous solution

Summary The decay kinetics of ascorbic acid radicals have been investigated in waters and juices of widely varying natural mineral composition. Both groups of beverages are characterised by specific kinetic behaviours. For mineral waters the half life (t _1/2) of the radical is 10–20 min, whilst for juicest _1/2, is reduced to 3-10 min in the pH ranges of 7–8.8 and 8–9, respectively.

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Über den Einfluß von natürlichen Mineralwässern und Fruchtsäften auf den Zerfall von Ascorbinsäure-Radikalen in wäßriger Lösung

Zusammenfassung Die Zerfallskinetik der Ascorbinsäure-Radikale wurde in Wässern und Fruchtsäften von breit gestreuter mineralischer Zusammensetzung untersucht. Beide Getränkegruppen werden durch spezifisches kinetisches Verhalten charakterisiert. Für Mineralwässer beträgt die Halbwertszeit (t _1/2) für das Radikal 10–20 min, während für Säftet _1/2 auf 3–10 min in den pH-Gebieten 7–8, 8 bzw. 8–9 reduziert wird.

     

Occurrence of natural and synthetic glucocorticoids in sewage treatment plants and receiving river waters

This paper first reports the occurrence of sixglucocorticoids (prednisone, prednisolone, cortisone, cortisol, dexamethasone, and 6alpha-methylprednisolone) in sewage treatment plants (STPs) and receiving rivers by establishing a method for analyzing glucocorticoids in complex environmental waters. For the various types of aqueous matrices considered, the absolute recoveries were from 73 to 99%, and limits of quantification were below 0.2 ng/L. Among the seven STPs studied, the average concentrations of prednisone, prednisolone, cortisone, cortisol, dexamethasone, and 6alpha-methylprednisolone in influents were, respectively, 2.6 +/- 2.1, 3.0 +/- 1.6, 30 +/- 21, 39 +/- 26, 1.2 +/- 0.70, and 0.62 +/- 0.65 ng/L, and their percent removals were 99 +/- 3.1, 78 +/- 8.8, 99 +/- 1.2, 98 +/- 2.5, 99 +/- 1.8, and 100 +/- 0%, respectively. The lower removal of prednisolone was found to be due to its relatively low efficiency of biodegradation, especially in anoxic and aerobic units. The frequently detected glucocorticoids in effluents were prednisolone, cortisol, and cortisone with average concentrations 0.56 +/- 0.06, 0.50 +/- 0.33, and 0.26 +/- 0.10 ng/ L. In the receiving waters, the Tonghui and Qing Rivers, the concentrations of these compounds in some samples were much higher than those in their corresponding STP effluents; these differences depended on the sampling date, suggesting that there was random discharging of untreated wastewaters into these rivers. In addition, the ratio between the combined concentrations of two natural glucocorticoids (cortisol and cortisone) and the concentration of one synthetic glucocorticoid, prednisolone, was found to be a potential index to reflect the wastewater discharging.     

Forces between colloid particles in natural waters

The origin and nature of interparticle forces acting on colloid surfaces in natural waters has been examined using an atomic force microscope. Natural colloids were represented by a surface film of iron oxide precipitated onto spherical SiO2 particles, and the effects of adsorbed natural organic matter (NOM), solution pH, and ionic composition on the force-separation curves were investigated. NOM from both riverine and marine environments was strongly adsorbed to the iron oxide surface. Under conditions of low ionic strength, the interparticle forces were dominated by electrostatic repulsion arising from negative functional groups on the NOM, except at very small separations (<10 nm) where repulsive forces arising from steric interference of the NOM molecules were also present. At high ionic strength (e.g., seawater) or low pH, the electrostatic forces were largely absent, allowing steric repulsion forces to dominate. In addition, adhesive bridging between surfaces by adsorbed NOM was observed, creating a strong energy barrier to spontaneous disaggregation of colloid aggregates. Our results demonstrate that adsorbed NOM dominates the surface forces and thus stability with respect to aggregation of natural water colloids.     

Manganese in natural mineral waters from Germany

154 commercially available natural mineral waters were analysed for their content of dissolved manganese (Mn(II)). 114 bottles were marked “deironized” (geogenic iron removed). Unexpectedly, waters rich in mangenese were more frequent among the deironized waters than among the non-deironized ones. Almost 20% of all waters contained more than 0,20 mg/l Mn(II), a toxicologically justified limit value with respect to formula-fed infants. Two waters which were declared as “adapted for the preparation of infant food” contained even more than 1,0 mg/l Mn(II). It is proposed to legally prescribe the declaration of manganese on the bottle. For reasons of preventive public health care, waters with more than 0,20 mg/l Mn(II) are not considered as suitable for the preparation of infant food.     

Simulated solar light irradiation of mesotrione in natural waters

Photolysis is expected to be a major degradation process for pollutants in surface waters. We report here the first photodegradation study on mesotrione, a new triketone herbicide for use in maize. In a first step, we investigated the direct photolysis of mesotrione at 365 nm from a kinetic and analytical point of view. Mesotrione sensitizes its own oxidation through singlet oxygen formation and sensitizes the oxidation of H-donors through electron or H-atom transfer. In a second step, irradiation experiments were performed under conditions prevalent in the aqueous environment. Mesotrione in submicromolar concentrations was exposed to simulated sunlight, in addition to Suwannee River natural organic matter and/or nitrates. Suwannee River natural organic matter sensitizes the oxidation of mesotrione through the intermediacy of singlet oxygen, and the rate of mesotrione transformation is significantly enhanced for Suwannee River natural organic matter concentrations equal to or above 10 mg/L. Nitrates played a negligible role in SRNOM solutions.     

Bromate in chlorinated drinking waters: occurrence and implications for future regulation

Bromate is a contaminant of commercially produced solutions of sodium hypochlorite used for disinfection of drinking water. However, no methodical approach has been carried out in U.S. drinking waters to determine the impact of such contamination on drinking water quality. This study utilized a recently developed method for quantitation of bromate down to 0.05 microg/L to determine the concentration of bromate present in finished waters that had been chlorinated using hypochlorite. Forty treatment plants throughout the United States using hypochlorite in the disinfection step were selected and the levels of bromate in the water both prior to and following the addition of hypochlorite were measured. The levels of bromate in the hypochlorite feedstock were also measured and together with the dosage information provided by the plants and the amount of free chlorine in the feedstock, it was possible to calculate the theoretical level of bromate that would be imparted to the water. A mass balance was performed to compare the level of bromate in finished drinking water samples to that found in the corresponding hypochlorite solution used for treatment. Additional confirmation of the source of elevated bromate levels was provided by monitoring for an increase in the level of chlorate, a co-contaminant of hypochlorite, atthe same point in the treatment plant where bromate was elevated. This study showed that bromate in hypochlorite-treated finished waters varies across the United States based on the source of the chemical feedstock, which can add as much as 3 microg/L bromate into drinking water. Although this is within the current negotiated industry standard that allows up to 50% of the maximum contaminant level (MCL) for bromate in drinking water to be contributed by hypochlorite, it would be a challenge to meet a tighter standard. Given that distribution costs encourage utilities to purchase chemical feedstocks from local suppliers, utilities in certain regions of the United States may be put at a distinct disadvantage if future lower regulations on bromate levels in finished drinking water are put into place. Moreover, with these contaminant levels it would be almost impossible to lower the maximum permissible contribution to bromate in finished water from hypochlorite to 10% of the MCL, which is the norm for other treatment chemicals. Until this issue is resolved, it will be difficult to justify a lowering of the bromate MCL from its current level of 10 to 5 microg/L or lower.     

Optimized parameters for fluorescence-based verification of ballast water exchange by ships

Mid-ocean ballast water exchange is mandatory for ships discharging foreign ballast in US territorial waters in order to reduce the risk of biological invasions. However, a reliable tool for determining whether the procedure took place is lacking. We investigated chromophoric dissolved organic matter (CDOM) fluorescence as a tracer of mid-ocean exchange on nine research cruises out of Asia, Europe, and the USA, focusing on challenging source conditions (high salinity, low CDOM). Using parallel factor analysis, we identified nine independent fluorescent components present in varying concentrations in the ocean and in ballast water. One component was sufficient for predicting the coastal vs oceanic source of most ballast water samples. Across nine cruises, thresholds (1.7 and 0.7 ppb quinine sulfate equivalent units) at two fixed wavelength pairs (lambda(ex)/lambda(em) = 320/414 and 370/496 nm, respectively) discriminated coastal from oceanic ballast water in > 95% of samples (N = 514). Our results suggest that single- and dual-channel fluorometers could be optimized for verifying ballast water exchange.     

Enumerating sparse organisms in ships' ballast water: why counting to 10 is not so easy

To reduce ballast water-borne aquatic invasions worldwide, the International Maritime Organization and United States Coast Guard have each proposed discharge standards specifying maximum concentrations of living biota that may be released in ships' ballast water (BW), but these regulations still lack guidance for standardized type approval and compliance testing of treatment systems. Verifying whether BW meets a discharge standard poses significant challenges. Properly treated BW will contain extremely sparse numbers of live organisms, and robust estimates of rare events require extensive sampling efforts. A balance of analytical rigor and practicality is essential to determine the volume of BW that can be reasonably sampled and processed, yet yield accurate live counts. We applied statistical modeling to a range of sample volumes, plankton concentrations, and regulatory scenarios (i.e., levels of type I and type II errors), and calculated the statistical power of each combination to detect noncompliant discharge concentrations. The model expressly addresses the roles of sampling error, BW volume, and burden of proof on the detection of noncompliant discharges in order to establish a rigorous lower limit of sampling volume. The potential effects of recovery errors (i.e., incomplete recovery and detection of live biota) in relation to sample volume are also discussed.     

Biogenic phosphate minerals in manure: implications for phosphorus loss to surface waters

Phosphorus (P) is present in waterways throughout the United States at concentrations that impair water quality. Agriculture, particularly livestock production, has been identified as a major cause of this impairment Excess manure P applied to croplands has increased P losses in runoff, leading to surface water eutrophication. We conducted a long-term (36-week) incubation with poultry and dairy manures applied to a silt loam soil to elucidate mechanisms controlling manure P loss to water. Manures were applied to supply the same total P rate to soils with different antecedent plant-available P concentrations (soil test P). There was a strong synergistic effect between dairy manure and soil test P on water extractable P, while soil test P did not affect P loss from poultry manure-amended soils. Using scanning electron microscopy and energy dispersive X-ray spectroscopy, we found that poultry manure contained sparingly soluble calcium and magnesium phosphate minerals that controlled soil solution P concentrations, while dairy manure did not These minerals resemble other biogenic phosphate minerals. Our findings refute current assumptions that all manure P behaves similarly in soils and that organic forms control manure-soil P loss to water.     

Hydrophobicity and octanol-water partitioning of trace metals in natural waters

The hydrophobicities of dissolved Al, Cu, Mn, and Pb have been determined in various contaminated natural water samples by 1-octanol extraction and C18 column retention. Octanol extraction varied among the metals studied and between the environments sampled but, in general, was greatest for Pb, whose conditional octanol-water partition coefficient, Dow, exceeded unit value in some samples. In most cases, metal partition into octanol either increased with increasing pH or exhibited a maximum under near-neutral conditions. Although the order and pH-dependence of metal retention by the C18 columns was consistent with these observations, the extent of retention was generally greater than the extent of metal extraction by octanol, possibly because of interferences effected by the C18 column matrix. Speciation calculations and results of controlled experiments employing metals in the presence of model ligands suggest that metals may become hydrophobic either by neutralizing relatively hydrophilic ligands or by combining with ligands that are intrinsically hydrophobic themselves. Given that octanol solubility affords an upper estimate of lipophilicity, the results of this investigation may have important implications regarding our understanding of metal bioavailability and toxicity in natural waters.