Effervescence assisted dispersive liquid–liquid microextraction followed by microvolume UV-Vis spectrophotometric determination of surfactants in water

The novel and simple methods for the sensitive determination of cationic and anionic surfactants in water based on effervescence assisted dispersive liquid–liquid microextraction and microvolume UV-Vis spectrophotometry have been developed. The method involves ion-pair extraction of cationic and anionic surfactants with organic dyes (methyl orange and azure A, respectively) during the dispersion of extraction solvent (CHCl₃) by CO₂ bubbles which are formed by the injection of a mixture of the extraction solvent and proton donor solvent into the sample solution which contains carbonate-ions as effervescency agent. The analytical performance of the proposed procedure was compared with the conventional dispersive liquid–liquid microextraction. Appropriate experimental conditions for both methods were investigated. The absorbances of the colored extracts at wavelengths of 440 and 625 nm obey Beer's law within the range of 0.1–5.0 mg/L for both cationic and anionic surfactants. The limit of detection (LOD) obtained using the effervescence assisted extraction method was 30 µg/L for cationic and anionic surfactants. The proposed methods were successfully applied to determination of surfactants in water samples.     

Photodegradation of the antibiotic spiramycin studied by high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry

The degradation of spiramycin induced by ultraviolet (UV) irradiation was studied at pH 3–4, 6–7 and 8–9 using high-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry. Furthermore, the influence of hydrogen peroxide and oxygen on the photodegradation was investigated. Three degradation products were observed in the presence of oxygen and four in the absence of oxygen. The degradation kinetics were monitored as mass area-time curves, analyzed and described using subsequent follow-up reaction first-order models. The m/z values of the degradation products were determined to be 160, 322 and 366, the latter representing two separate products, the sugar moieties of spiramycin. Remainders of the macrocycle or the intact lactone ring of spiramycin were not observed, since the conjugated π-electron system was assumed photoexcited and thus undergoing photodegradation and fast destruction of the ring. The kinetic of the degradation of spiramycin itself was described using a first-order model. The degradation was accelerated upon addition of hydrogen peroxide. In contrast, systematic acceleration depending on pH could not be found. The absence of oxygen did not lead to any significant acceleration. The findings are interpreted in terms of the effectiveness of advanced oxidation processes and their potential use as a fourth purification step in wastewater treatment plants.     

Monitoring priority substances of directives 76/464/EEC and 2000/60/EC in Greek water bodies

The priority substances of List I, 76/464/EEC Directive, some of which belong to the new Water Framework Directive 2000/60/EC, have been monitored in the surface waters of Greece through the developed network of 53 sampling stations. The analytical methods used for the determination of these substances included Purge and Trap-Gas chromatography-Mass spectrometry for volatile and semivolatile organic compounds, Gas Chromatography-Electron Capture Detection for organochlorine insecticides, High Performance Liquid Chromatography for pentachlorophenol and Atomic Absorption Spectrometry for metals. The results have shown the presence of several priority substances in Greek surface waters, in most cases at concentrations well below the regulatory limits. However, non-compliance was observed for a limited number of compounds. The monitoring network and the analytical determinations have to be expanded to more water bodies and more priority substances, in order to safeguard the quality of Greek surface waters.     

Growth response of an early successional assemblage of coralline algae and benthic diatoms to ocean acidification

The sustained absorption of anthropogenically released atmospheric CO₂ by the oceans is modifying seawater carbonate chemistry, a process termed ocean acidification (OA). By the year 2100, the worst case scenario is a decline in the average oceanic surface seawater pH by 0.3 units to 7.75. The changing seawater carbonate chemistry is predicted to negatively affect many marine species, particularly calcifying organisms such as coralline algae, while species such as diatoms and fleshy seaweed are predicted to be little affected or may even benefit from OA. It has been hypothesized in previous work that the direct negative effects imposed on coralline algae, and the direct positive effects on fleshy seaweeds and diatoms under a future high CO₂ ocean could result in a reduced ability of corallines to compete with diatoms and fleshy seaweed for space in the future. In a 6-week laboratory experiment, we examined the effect of pH 7.60 (pH predicted to occur due to ocean acidification just beyond the year 2100) compared to pH 8.05 (present day) on the lateral growth rates of an early successional, cold-temperate species assemblage dominated by crustose coralline algae and benthic diatoms. Crustose coralline algae and benthic diatoms maintained positive growth rates in both pH treatments. The growth rates of coralline algae were three times lower at pH 7.60, and a non-significant decline in diatom growth meant that proportions of the two functional groups remained similar over the course of the experiment. Our results do not support our hypothesis that benthic diatoms will outcompete crustose coralline algae under future pH conditions. However, while crustose coralline algae were able to maintain their presence in this benthic rocky reef species assemblage, the reduced growth rates suggest that they will be less capable of recolonizing after disturbance events, which could result in reduced coralline cover under OA conditions.     

The imprecision in rates of down syndrome by 1-year maternal age intervals: A critical analysis of rates used in biochemical screening

Current algorithms to determine eligibility for prenatal cytogenetic diagnostic services depend critically on the accuracy and precision of the underlying rates of cytogenetic abnormality used in the calculations. We examine the maternal age-specific rates of Down syndrome livebirths in eight studies of European-origin populations, pooled rates from which are widely used for baseline calculations in biochemical screening. These studies vary significantly in such factors as methods of ascertainment of cases, likelihood of complete ascertainment, and methods of correction, if any, for underascertainment. Restriction of analysis to those two studies among the eight whose methods suggest the greatest likelihood of complete ascertainment for Down syndrome generates rates significantly higher than those in widespread use. Confidence intervals about previously reported and currently derived rates indicate that even with large-scale data, there is considerable residual uncertainty in derived rates.     

Habitat associations and diet of young-of-the-year Pacific cod (<Emphasis Type="Italic">Gadus macrocephalus</Emphasis>) near Kodiak,Alaska

The influence of environmental variables and habitat on growth and survival of juvenile gadoid species in the Atlantic has been clearly demonstrated; conversely, in the North Pacific little is known about the habitat and ecology of juvenile Pacific cod (Gadus macrocephalus Tilesius). The hypothesis that density of young-of-the-year (YOY) Pacific cod in nearshore habitats is predicted by shallow depth and the presence of eelgrass and macroalgae was tested in a variety of nearshore habitats adjacent to commercial fishing grounds near Kodiak Island, AK. From 10 to 22 August 2002, a beach seine and small-meshed beam trawl were used to capture YOY Pacific cod (n = 254) ranging from 42 to 110 mm fork length. Depth, water temperature, salinity, sediment grain size, and percent cover by emergent structure (i.e. tube-dwelling polychaetes, sea cucumber mounds, macroalgae) were measured prior to fishing. Density of YOY Pacific cod was highest in areas of moderate depth (15–20 m) and positively and linearly related to percent cover by sea cucumber mounds and to salinity. No previous studies have documented fish utilizing sea cucumber mounds as habitat. Furthermore, eelgrass and macroalgae were inconsequential to cod distribution. Diets consisted mainly of small calanoid copepods, mysids, and gammarid amphipods and were significantly related to cod length and depth. This work provides important information on previously undocumented factors that affect distribution and feeding of YOY Pacific cod, which ultimately influence growth and survival in this species.     

Plants control the seasonal dynamics of microbial N cycling in a beech forest soil by belowground C allocation

Soil microbes in temperate forest ecosystems are able to cycle several hundreds of kilograms of N per hectare per year and are therefore of paramount importance for N retention. Belowground C allocation by trees is an important driver of seasonal microbial dynamics and may thus directly affect N transformation processes over the course of the year. Our study aimed at unraveling plant controls on soil N cycling in a temperate beech forest at a high temporal resolution over a time period of two years, by investigating the effects of tree girdling on microbial N turnover. In both years of the experiment, we discovered (1) a summer N mineralization phase (between July and August) and (2) a winter N immobilization phase (November-February). The summer mineralization phase was characterized by a high N mineralization activity, low microbial N uptake, and a subsequent high N availability in the soil. During the autumn/winter N immobilization phase, gross N mineralization rates were low, and microbial N uptake exceeded microbial N mineralization, which led to high levels of N in the microbial biomass and low N availability in the soil. The observed immobilization phase during the winter may play a crucial role for ecosystem functioning, since it could protect dissolved N that is produced by autumn litter degradation from being lost from the ecosystem during the phase when plants are mostly inactive. The difference between microbial biomass N levels in winter and spring equals 38 kg N/ha and may thus account for almost one-third of the annual plant N demand. Tree girdling strongly affected annual N cycling: the winter N immobilization phase disappeared in girdled plots (microbial N uptake and microbial biomass N were significantly reduced, while the amount of available N in the soil solution was enhanced). This was correlated to a reduced fungal abundance in autumn in girdled plots. By releasing recently fixed photosynthates to the soil, plants may thus actively control the annual microbial N cycle. Tree belowground C allocation increases N accumulation in microorganisms during the winter which may ultimately feed back on plant N availability in the following growing season.     

Development and Validation of an Aquatic Fine Sediment Biotic Index

The Fine Sediment Biotic Index (FSBI) is a regional, stressor-specific biomonitoring index to assess fine sediment (<2 mm) impacts on macroinvertebrate communities in northwestern US streams. We examined previously collected data of benthic macroinvertebrate assemblages and substrate particle sizes for 1,139 streams spanning 16 western US Level III Ecoregions to determine macroinvertebrate sensitivity (mostly at species level) to fine sediment. We developed FSBI for four ecoregion groupings that include nine of the ecoregions. The grouping were: the Coast (Coast Range ecoregion) (136 streams), Northern Mountains (Cascades, N. Rockies, ID Batholith ecoregions) (428 streams), Rockies (Middle Rockies, Southern Rockies ecoregions) (199 streams), and Basin and Plains (Columbia Plateau, Snake River Basin, Northern Basin and Range ecoregions) (262 streams). We excluded rare taxa and taxa identified at coarse taxonomic levels, including Chironomidae. This reduced the 685 taxa from all data sets to 206. Of these 93 exhibited some sensitivity to fine sediment which we classified into four categories: extremely, very, moderately, and slightly sensitive; containing 11, 22, 30, and 30 taxa, respectively. Categories were weighted and a FSBI score calculated by summing the sensitive taxa found in a stream. There were no orders or families that were solely sensitive or resistant to fine sediment. Although, among the three orders commonly regarded as indicators of high water quality, the Plecoptera (5), Trichoptera (3), and Ephemeroptera (2) contained all but one of the species or species groups classified as extremely sensitive. Index validation with an independent data set of 255 streams found FSBI scores to accurately predict both high and low levels of measured fine sediment.     

Investigation of sequential and enzymatic extraction of arsenic from drinking water distribution solids using ICP-MS

A sequential extraction approach was utilized to estimate the distribution of arsenite [As(iii)] and arsenate [As(v)] on iron oxide/hydroxide solids obtained from drinking water distribution systems. The arsenic (As) associated with these solids can be segregated into three operationally defined categories (exchangeable, amorphous and crystalline) according to the sequential extraction literature. The exchangeable As, for the six drinking water solids evaluated, was estimated using 10 mM MgCl(2) and 10 mM NaH(2)PO(4) and represented between 5-34% of the total As available from the solid. The amorphously bound As was estimated using 10 mM (NH(4))(2)C(2)O(4) and represented between 57-124% of the As available from the respective solid. Finally, the crystalline bound As was estimated using titanium citrate and this represented less than 1.5% of the As associated with the solids. A synthetic stomach/intestine extraction approach was also applied to the distribution solids. The stomach fluid was found to extract between 0.5-33.3 microg g(-1) As and 120-2,360 microg g(-1) iron (Fe). The As concentrations in the intestine fluid were between 0.02-0.04 microg g(-1) while the Fe concentration ranged from 0.06-0.7 microg g(-1) for the first six drinking water distribution solids. The elevated Fe levels associated with the stomach fluid were found to produce Fe based precipitates when the intestinal treatment was applied. Preliminary observations indicate that most of the aqueous Fe in the stomach fluid is ferric ion and the observed precipitate produced in the intestine fluid is consistent with the decreased solubility of ferric ion at the pH associated with the intestine.