Development of an ombrotrophic peat bog (low ash) reference material for the determination of elemental concentrations

Given the increasing interest in using peat bogs as archives of atmospheric metal deposition, the lack of validated sample preparation methods and suitable certified reference materials has hindered not only the quality assurance of the generated analytical data but also the interpretation and comparison of peat core metal profiles from different laboratories in the international community. Reference materials play an important role in the evaluation of the accuracy of analytical results and are essential parts of good laboratory practice. An ombrotrophic peat bog reference material has been developed by 14 laboratories from nine countries in an inter-laboratory comparison between February and October 2002. The material has been characterised for both acid-extractable and total concentrations of a range of elements, including Al, As, Ca, Cd, Cr, Cu, Fe, Hg, Mg, Mn, Na, Ni, P, Pb, Ti, V and Zn. The steps involved in the production of the reference material (i.e. collection and preparation, homogeneity and stability studies, and certification) are described in detail.     

Prolonged reproductive consequences of short-term biomass loss in seaweeds

This study describes the reproductive collapse of a large giant-kelp forest (Macrocystis pyrifera; Point Loma, southern California, USA) and the dynamics of its subsequent recovery. High-frequency sampling within a 100-m² area, combined with a 3-year reproduction time-series from four other sites over a broad depth gradient, were used to (1) quantify temporal and spatial patterns of change in size and fertility of adult sporophytes, and (2) examine physical and biological factors that regulate such changes. Giant-kelp sporophytes have the potential for continuous reproduction, yet from March to November 1999, sporophytes at the high-frequency sampling site went from completely sloughing (actively releasing zoospores) to completely sterile, despite a relatively constant biomass of sporogenous tissues. This shift to sterility was rapid, with 65% of sporophytes ceasing to slough during late-June/early-July 1999, and did not co-occur with stressful physical conditions (i.e. high temperatures, low nutrients, or high wave intensity). Instead, the cessation of reproductive output corresponded to an episodic, sublethal amphipod-grazing event that stripped blade biomass from all sporophytes. Although the grazer infestation affected the entire kelp forest, peaks in grazer abundance were localized, moving through the population during late spring and summer, and causing patchiness in sporophyte size and fertility on a scale of meters. The reproductive collapse was size-dependent, since smaller sporophytes were the first to cease sloughing. The grazing event waned in the fall and sporophyte vegetative growth rapidly recovered lost biomass (within ~2 months). Such growth, however, occurred at the expense of the production of sporogenous tissue and caused a prolonged period (>4 months) of decreased reproductive output. These results suggest a trade-off between sporophyte growth and reproduction, allowing short-term disturbances to have lasting impacts on the reproductive output of giant-kelp populations.     

Degradation of octylphenol and nonylphenol by ozone - part I: direct reaction

This aqueous reaction between ozone and two alkylphenols (APs), namely octylphenol (OP) and nonylphenol (NP), has been investigated. Both compounds are important endocrine disrupting chemicals, which arise from the biodegradation of alkylphenol ethoxylates and are often found at relatively high concentrations in wastewater effluents. In this paper the results of an experimental study are presented which provide values for the reaction rate constants between molecular ozone and undissociated OP and NP, and overall reaction rate constants for the degradation of the two APs at pH values in the range of 7-9. The kinetic rate constants for OP and NP degradation by molecular ozone were 4.33(+/-0.18) x 10(4) and 3.90(+/-0.10) x 10(4) M(-1) s(-1), and the reaction stoichiometry was similar in both cases and equal to approximately 1.3:1 ([O3]:[AP]). The overall second order reaction rate constants for the two APs increased significantly with increasing pH, which is believed to be mainly due to the increasing influence of indirect radical reaction with increasing pH; this aspect is considered in more detail in a companion paper. A preliminary investigation of the reaction mechanism suggests that an initial product of ozonation is hydroxyl-alkyl phenol.     

Contribution of vehicle emissions from an attached garage to residential indoor air pollution levels

The infiltration of vehicle emissions into a house from the attached garage was studied for 16 homes of differing designs using the same extensively characterized vehicle at each home. Before the in-home measurement program, the cold-start and hot-start tailpipe emissions and hot-soak evaporative emissions from a 1993 Buick Regal were measured using standard vehicle emissions measurement methods. The emissions were chemically characterized for methane, nonmethane hydrocarbons (NMHC), and carbonyl compounds. The in-home measurements occurred over two winter seasons (1997-1998 and 1998-1999) in Ottawa, Ontario, Canada. Samples of indoor air and garage atmosphere were characterized for carbon monoxide, carbon dioxide, methane, NMHC, and carbonyl compounds. During the second year, real-time measurements of carbon, carbon dioxide, and total hydrocarbons were made to determine when and for how long the emissions plume infiltrates the house. Chemical mass balance modeling results using 31 NMHC species suggest that between 9 and 71% of the concentrations measured in the house during the hot-soak test and between 13 and 85% of the concentrations measured in the house during the cold-start test could be attributed to vehicle emissions infiltrating from the garage. In contrast, increases in carbonyl compound concentrations caused by the vehicle were difficult to detect above the already significant levels found in the houses.     

Effects of skin and hydraulic fractures on SVE wells

Soil vapor extraction (SVE) systems are intended to cause substantial volumes of air to flow through the subsurface with the purpose of removing volatile contaminants. The effectiveness of SVE can be influenced by any effect that changes the specific gas capacity (discharge as a function of vacuum) of a well. Skins of low permeability material enveloping a well bore are widely recognized to affect the performance of wells used to recover water, natural gas, or petroleum, and skin can also significantly diminish the performance of an SVE well. Skins a few mm thick consisting of material whose gas phase permeability is 0.01 of the formation can reduce the specific gas capacity of an SVE well by factors of 2 to 10 or more. Hydraulic fractures created in the vicinities of shallow wells commonly resemble sand-filled layers shaped like flat-lying disks or gently dipping saucers. The contrast between the gas-phase permeability of the sand in the fracture and that of the formation is particularly important, with significant effects requiring the ratio to be greater than approximately 50. Shallow hydraulic fractures filled with several tenths of m3 of sand in formations that are several orders of magnitude less permeable than that of the enveloping formation should increase specific gas capacity by factors of 10 or more. Field tests of the effects of hydraulic fractures on the performance of SVE were conducted by creating four wells intersecting fractures and a suite of control wells created using conventional methods in silty saprolite. Specific gas capacities ranged over more than an order of magnitude for 10 wells completed within a small area (2 m2) and at the same depth. Specific capacities correlate to the drilling method that was used to create the bore for the well: lowest values occurred in wells drilled with a machine auger, slightly better results were obtained using a Shelby tube, and the best results were obtained from conventional wells bored with a hand auger. Skin factors determined for wells created with a machine auger could be explained by a layer 1 cm thick that has 0.007 times the permeability of the enveloping material, which could readily have been created during the drilling procedure. Specific capacities of wells intersecting hydraulic fractures were 5 to 100 times more than those of conventional wells. The large difference in performance appears to be due in part to the beneficial effects of the fracture, and in part to the detrimental effects of well skin.     

Appraisal of visual assessments of habitat complexity and benthic composition on coral reefs

Visual assessments of topographic habitat structure and benthos on coral reefs were appraised using quantitative data collected from 16 replicate surveys within each of 21 sites on Seychelles reefs. Results from visual assessments of reef benthos were similar to those obtained using techniques frequently used to assess benthic complexity and composition. Visual estimates of habitat topography were correlated with rugosity, reef height and holes of 10–70 cm diameter, whilst visual estimates of benthic composition were very similar to those obtained from line intercept transects. Visual estimates of topography correlated strongly with species richness of fish communities and explained 42% of the variation in these data. The relationship between visual estimates of topography and species richness is strongest with fish 10–30 cm total length (TL), abundance of fish within this size category also correlating positively with topographic visual assessments. Visual techniques are prone to observer bias, however with regular training they can be used to quickly provide a reliable and effective means of assessing habitat complexity and benthos on coral reefs.     

Chorionic villus sampling for prenatal diagnosis in wales using DNA probes—5 years' experience

Chorionic villi were sampled from 125 women who requested prenatal diagnosis, either for genetic disorders or because of advanced maternal age. Of these, 105 samples were obtained by the transcervical route and 20 were obtained by the transabdominal approach. The sampling success rate was 97 per cent (122/125). The mean maternal age of the patients was 31 years (range 17–44) and the mean gestational age at which the chorionic villus sampling was performed was 10 weeks (range 7–13 weeks). Seventy-four of these diagnoses involved the use of DNA markers. The minimal size of the sample used for DNA diagnosis was 5 mg. Maternal contamination was detected in two samples. A diagnosis was provided on all but two samples. The fetal loss rate was high initially but fell to 1·9 per cent in 1988.     

Correlations between in situ denitrification activity and nir-gene abundances in pristine and impacted prairie streams

Denitrification is a process that reduces nitrogen levels in headwaters and other streams. We compared nirS and nirK abundances with the absolute rate of denitrification, the longitudinal coefficient of denitrification (i.e., K_den, which represents optimal denitrification rates at given environmental conditions), and water quality in seven prairie streams to determine if nir-gene abundances explain denitrification activity. Previous work showed that absolute rates of denitrification correlate with nitrate levels; however, no correlation has been found for denitrification efficiency, which we hypothesise might be related to gene abundances. Water-column nitrate and soluble-reactive phosphorus levels significantly correlated with absolute rates of denitrification, but nir-gene abundances did not. However, nirS and nirK abundances significantly correlated with K_den, as well as phosphorus, although no correlation was found between K_den and nitrate. These data confirm that absolute denitrification rates are controlled by nitrate load, but intrinsic denitrification efficiency is linked to nirS and nirK gene abundances.     

The changing nature of the 206Pb/207Pb isotopic ratio of lead in rainwater, atmospheric particulates, pine needles and leaded petrol in Scotland, 1982-1998

The inductively coupled plasma-mass spectrometry (ICP-MS)-determined 206Pb/207Pb ratio of 145 samples of rainwater collected at 25 locations around Scotland during December 1997 and January 1998 and at three longterm monitoring stations in the northeast, central belt and southeast of the country from November 1997 to December 1998 averaged 1.144+/-0.017 (1 s). This represents a significant increase from the mean value of 1.120+/-0.016 recorded for the long-term sites in 1989 1991, only partly attributable to a concomitant increase in the 206Pb/207Pb ratio of leaded petrol from 1.075+/-0.013 to 1.088+/-0.007. The rainwater 206Pb/207Pb data for the late 1990s also contrast markedly with the lower 206Pb/207Pb ratios found for pine needle and atmospheric particulate samples from Scotland (e.g. Glasgow: 1.085+/-0.012 in 1985-1986, 1.099+/-0.007 in 1991-1992), England and Western Europe in this study for the period 1982-1992 when emissions of lead to the atmosphere from petrol-engined vehicles in the UK were approximately 2-9 times higher. The observed change in the lead isotopic signature of rainwater predominantly reflects the impact of measures, such as the introduction and growing uptake of unleaded petrol, to reduce car exhaust emissions of lead to the atmosphere in the UK. Based on the rainwater data, source apportionment calculations suggest a general decline in the contribution of leaded petrol to atmospheric lead in Scotland from 53-61% in 1989-1991 to 32-45% in 1997-1998, with a corresponding decline in the urban environment from 84-86% to 48-58%.