Size distribution and composition of phosphorus in the East Tiao River, China: the significant role of colloids

The environmental risk of aquatic phosphorus (P) critically depends on its mobility and bioavailability, both of which are greatly affected by the size distribution and composition of P. The size distribution (particulate, colloidal and truly dissolved phase) of P, composed of molybdate reactive P (MRP) and molybdate unreactive P (MUP), was determined at twenty-three typical sections of the East Tiao River, China in the plum rain season. Results indicated particulate P was dominant followed by the truly dissolved P, while colloidal P was quantitatively the lowest in the whole river. From upstream to downstream, particulate P sharply increased, along with a slight decrease of truly dissolved P. However, colloidal P remained at a relatively stable level in the whole river, ranging from below detection limit to 0.025 mg L(-1), 0 to 13.4% of total P (TP). Furthermore, colloidal MRP exhibited a rising trend downriver as compared to upriver, with the notable transfer of MRP from the truly dissolved phase to particulate and colloidal phases. Particle concentration effect for colloids, observed in the study of MRP distribution, further corroborated the role of colloids in MRP solid/liquid partitioning. These observations, in this large-scale field investigation, fitted the "colloidal pumping" hypothesis. It may be concluded that colloids act as the intermediate and buffer in the dynamically balanced transfer of P from truly dissolved phase to large particulate phase, having a significant role in size distribution of P.     

Determination of total and EDTA extractable metal distributions in the colloidal fraction of contaminated soils using SdFFF-ICP-HRMS

Newly developed methods involving an on-line combination of sedimentation field-flow fractionation-inductively coupled plasma-high resolution mass spectrometry (SdFFF-ICP-HRMS) have been used to study the distributions of extractable heavy metals in a soil which had been treated with sewage sludge contaminated with Cu or Pb. The relationship of these metals with other elements in the colloidal fraction was also investigated. The colloidal fraction from the soil was obtained by repeated gravitational sedimentation and extracted with 0.11 M acetic acid, 0.1 M hydroxylamine hydrochloride, 0.05 M ethylenediaminetetraacetic acid disodium salt (EDTA) or aqua regia to assess the potential availability of the metals Cu and Pb. Large proportions of the Cu and Pb were extracted by EDTA, approaching that removed by aqua regia, whereas < 10% of the aqua regia extractable metals were removed by acetic acid and hydroxylamine chloride. The distributions of the heavy metals, the major mineral forming element (Al) and the elements forming sesquioxides (Fe and Mn) within different size classes (0.05-1 microm) of the colloidal fraction were measured using SdFFF-ICP-HRMS before and after extraction with EDTA. This information provides an insight into the composition of the colloids and the distributions of metal contaminants. In the contaminated soil colloids, the concentration of Fe, Mn and Pb is greatest in the smaller particles (<0.2 microm). In contrast, the Cu concentration is constant over the size range studied. Iron oxide surface coatings probably play a significant role in Pb adsorption on soil particles, but may be less important for Cu. The combination of selective chemical extraction, SdFFF and ICP-HRMS provides a means of determining the distribution of potentially available heavy metals within the colloidal fraction of contaminated soils.     

Chromium speciation and fractionation in ground and surface waters in the vicinity of chromite ore processing residue disposal sites

Chromium concentrations of up to 91 mg l(-1) were found by ICP-OES for ground water from nine boreholes at four landfill sites in an area of S.E. Glasgow/S. Lanarkshire where high-lime chromite ore processing residue (COPR) from a local chemical works had been deposited from 1830 to 1968. Surface water concentrations of up to 6.7 mg l(-1) in a local tributary stream fell to 0.11 mg l(-1) in the River Clyde. Two independent techniques of complexation/colorimetry and speciated isotope dilution mass spectrometry (SIDMS) showed that Cr was predominantly (>90%) in hexavalent form (CrVI) as CrO4(2-), as anticipated at the high pH (7.5-12.5) of the sites. Some differences between the implied and directly determined concentrations of dissolved CrIII, however, appeared related to the total organic carbon (TOC) content. This was most significant for the ground water from one borehole that had the highest TOC concentration of 300 mg l(-1) and at which < 3% of Cr was in the form of CrVI. Subsequent ultrafiltration produced significant decreases in Cr concentration with decreasing size fractions, e.g. <0.45 microm, < 100 kDa, <30 kDa and < 1 kDa by the tangential-flow method. As this appeared related more to concentrations of humic substances than of TOC per se, horizontal bed gel electrophoresis of freeze-dried ultrafilter retentates was carried out to further characterise the CrIII-organic complex. This showed for the main Cr-containing fraction, 100 kDa-0.45 microm, that the Cr was associated with a dark brown band characteristic of organic (humic) matter. Comparison of gel electrophoresis and FTIR results for ultrafilter retentates of ground water from this borehole with those for a borehole at another site where CrVI predominated suggested the influence of carboxylate groups, both in reducing CrVI and in forming soluble CrIII-humic complexes. The implications of this for remediation strategies (especially those based on the addition of organic matter) designed to reduce highly mobile and carcinogenic Cr(VI)O4(2-) to the much less harmful CrIII as insoluble Cr(OH)3 are discussed.     

Estuarine mixing behavior of colloidal organic carbon and colloidal mercury in Galveston Bay, Texas

Mercury (Hg) in estuarine water is distributed among different physical phases (i.e. particulate, colloidal, and truly dissolved). This phase speciation influences the fate and cycling of Hg in estuarine systems. However, limited information exists on the estuarine distribution of colloidal phase Hg, mainly due to the technical difficulties involved in measuring it. In the present study, we determined Hg and organic carbon levels from unfiltered, filtered (<0.45 μm), colloidal (10 kDa-0.45 μm), and truly dissolved (<10 kDa) fractions of Galveston Bay surface water in order to understand the estuarine mixing behavior of Hg species as well as interactions of Hg with colloidal organic matter. For the riverine end-member, the colloidal fraction comprised 43 ± 11% of the total dissolved Hg pool and decreased to 17 ± 8% in brackish water. In the estuarine mixing zone, dissolved Hg and colloidal organic carbon showed non-conservative removal behavior, particularly in the low salinity (<15 ppt) region. This removal may be caused by salt-induced coagulation of colloidal matter and consequent removal of dissolved Hg. The particle-water interaction, K(d) ([particulate Hg (mol kg(-1))]/[dissolved Hg (mol L(-1))]) of Hg decreased as particle concentration increased, while the particle-water partition coefficient based on colloidal Hg and the truly dissolved Hg fraction, K(c) ([colloidal Hg (mol kg(-1))]/[truly dissolved Hg (mol L(-1))]) of Hg remained constant as particle concentration increased. This suggests that the particle concentration effect is associated with the amount of colloidal Hg, increasing in proportion to the amount of suspended particulate matter. This work demonstrates that, colloidal organic matter plays an important role in the transport, particle-water partitioning, and removal of dissolved Hg in estuarine waters.     

Colloidal mercury (Hg) distribution in soil samples by sedimentation field-flow fractionation coupled to mercury cold vapour generation atomic absorption spectroscopy

Diverse analytical techniques are available to determine the particle size distribution of potentially toxic elements in matrices of environmental interest such as soil, sediments, freshwater and groundwater. However, a single technique is often not exhaustive enough to determine both particle size distribution and element concentration. In the present work, the investigation of mercury in soil samples collected from a polluted industrial site was performed by using a new analytical approach which makes use of sedimentation field-flow fractionation (SdFFF) coupled to cold vapour generation electrothermal atomic absorption spectroscopy (CV-ETAAS). The Hg concentration in the SdFFF fractions revealed a broad distribution from about 0.1 to 1 μm, roughly following the particle size distributions, presenting a maximum at about 400-700 nm in diameter. A correlation between the concentration of Hg in the colloidal fraction and organic matter (O.M.) content in the soil samples was also found. However, this correlation is less likely to be related to Hg sorption to soil O.M. but rather to the presence of colloidal mercuric sulfide particles whose size is probably controlled by the occurrence of dissolved O.M. The presence of O.M. could have prevented the aggregation of smaller particles, leading to an accumulation of mercuric sulfides in the colloidal fraction. In this respect, particle size distribution of soil samples can help to understand the role played by colloidal particles in mobilising mercury (also as insoluble compounds) and provide a significant contribution in determining the environmental impact of this toxic element.     

The simultaneous modelling of metal ion and humic substance transport in column experiments

Pulsed column experiments using Co, fulvic acid and porous sediment packing, along with up/down-flooding experiments using Eu, humic acid and intact sandstone blocks have been performed. The elution of metal and humic and their distribution along the sandstone columns have been measured. A mixed equilibrium and kinetic coupled chemical transport model has been used to simulate the results. In both cases, one exchangeable and one non-exchangeable component have been used to simulate the interaction of metal and humic substance. For the pulsed experiments, a simple equilibrium approach was used to model humic sorption, while a two component, kinetic model was required for the sandstone columns.     

Sorption and desorption of benzo(a)pyrene in aquatic systems

The sorptive behaviour of polycyclic aromatic hydrocarbons (PAHs) is critical to controlling their transport, fates and effects in the environment. Experiments are described which detail the behaviour of a model compound (benzo(a)pyrene) under simulated aquatic conditions. The kinetics of sorption were comparable to those of other PAH compounds. The sorption equilibrium was extensively studied and found to be affected by several key parameters, notably sediment concentration. The sorption coefficient decreased substantially with the sediment concentration, from 9580 ml g(-1) at a sediment concentration of 0.067 g l(-1) to 1,110 ml g(-1) at a sediment concentration of 9.8 g l(-1). The results are consistent with previous reports and often explained by the presence of colloids. In this paper the dry weight concentration of colloids was determined and used for deriving the true sorption coefficient, which is up to an order of magnitude higher than the observed partition coefficient. The sorption of benzo(a)pyrene was also dependent on some of the particle properties, and the sorption coefficient was found to increase with the organic carbon content and specific surface area of sediment particles. The desorption of benzo(a)pyrene from sediment was shown to be relatively rapid, with implications for the potential remobilisation of benzo(a)pyrene and similar compounds.     

Adsorption of antimony(V) by floodplain soils, amorphous iron(III) hydroxide and humic acid

Antimony (Sb) emissions to the environment are increasing, and there is a dearth of knowledge regarding Sb fate and behaviour in natural systems. In particular, there is a lack of understanding of sorption of the oxidised Sb(V) species onto soils and soil phases. In this study sorption of Sb(V) by two organic rich soils with high levels of oxalate extractable Fe was examined over the pH range of 2.5-7. Furthermore, the sorption behaviour of Sb(V) was examined in two phases mimicking those dominant in the experimental soils, namely a solid humic acid and an amorphous Fe(OH)3, across the same pH range. Sorption of Sb by the soils and the humic acid fitted a Freundlich type isotherm, with the equation parameters reflecting changes in bonding affinity corresponding to pH changes. The soils sorbed >75% of the added Sb in all trials, and 80-100% at pH values less than approximately 6.5. The Fe(OH)3 retained >95% of the added Sb in all experiments. The humic acid sorbed up to 60% of the added Sb at acidic pH values, but sorption decreased to zero at higher pH values. Further adsorption studies are recommended, such as examining the effects of ion competition and changes in ionic strength.     

Water quality mapping and assessment, and weathering processes of selected aflaj in Oman

There are more than 4,000 falaj (singular of a peculiar dug channel) distributed in different regions in Oman. The chemical characteristics of the water in 42 falaj were studied to evaluate the major ion chemistry; geochemical processes controlling water composition; and suitability of water for drinking, domestic, and irrigation uses. GIS-based maps indicate that the spatial distribution of chemical properties and concentrations vary within the same region and the different regions as well. The molar ratios of (Ca + Mg)/Total cations, (Na + K)/Total cations, (Ca + Mg)/(Na + K), (Ca + Mg)/(HCO? + SO?), and Na/Cl reveal that the water chemistry of the majority of aflaj are dominated by carbonate weathering and evaporite dissolution, with minor contribution of silicate weathering. The concentrations of most of the elements were less than the permissible limits of Omani standards and WHO guidelines for drinking water and domestic use and do not generally pose any health and environmental problems. Some aflaj in ASH Sharqiyah and Muscat regions can be used for irrigation with slight to severe restriction because of the high levels of electrical conductivity, total dissolved solids, chloride, and sodium absorption ratio.     

Hydrochemical and water quality assessment of groundwater in Doon Valley of Outer Himalaya, Uttarakhand, India

The present study discusses ion sources and assesses the chemical quality of groundwater of Doon Valley in Outer Himalayan region for drinking and irrigational purposes. Valley is almost filled with Doon gravels that are main aquifers supplying water to its habitants. Recharged only by meteoric water, groundwater quality in these aquifers is controlled essentially by chemical processes occurring between water and lithology and locally altered by human activities. Seventy-six water samples were collected from dug wells, hand pumps and tube wells and were analysed for their major ion concentrations. The pH is varying from 5.6 to 7.4 and electrical conductivity from 71 to 951 μmho/cm. Groundwater of Doon valley is dominated by bicarbonate contributing 83% in anionic abundance while calcium and magnesium dominate in cationic concentrations with 88%. The seasonal and spatial variation in ionic concentration, in general, is related to discharge and lithology. The high ratio of (Ca + Mg)/(Na + K), i.e. 10, low ratio of (Na + K)/TZ+, i.e.0.2 and also the presence of carbonate lithology in the northern part of valley, is indicative of carbonate dissolution as the main controlling solute acquisition process in the valley. The low abundance of silica content and high HCO?/H?SiO? ratio also supports carbonate dissolution and less significant role of silicate weathering as the major source for dissolved ions in Doon Valley. The analytical results computed for various indices show that water is of fairly good quality, although, hard but have moderate dissolved solid content. It is free from sodium hazard lying in C?-S? and C?-S? class of USSL diagram and in general suitable for drinking and irrigation except few locations having slightly high salinity hazard.     

Kinetics of sorption of lead on bed sediments of River Hindon, India

A number of low cost waste sorbent have been used for removal of heavy metals, however, few studies have been carried out on the sorption process on riverbed sediments in their natural state of occurrence. Stream sediments adsorb certain solutes from streams, thereby significantly changing the solute composition, but little is known about quantitatively describing sorption phenomena and rates of these processes. In the present investigation, sorption of lead ions on river bed sediments of river Hindon, a tributary of river Yamuna, India has been studied to demonstrate the role of bed sediments in controlling metal pollution. The effect of various operating variables, viz., initial concentration, solution pH, sediment dose, contact time and particle size has been studied. The sorption of lead ions increased with respect to pH and sorbent dose and decreased with sorbent particle size. Two important geochemical phases, iron and manganese oxide, also play important role in the sorption process. The sorption data were analysed using Langmuir and Freundlich isotherm models to determine the mechanistic parameters related to the sorption process. Further, although lead ions have more affinity for the fine fraction of the sediment, but the overall contribution of coarser fraction to sorption is more as compared to clay and silt fraction. The kinetic data suggest that the sorption of lead on bed sediments is an endothermic process, which is spontaneous at low temperature. The uptake of lead is controlled by both bulk and intraparticle diffusion mechanism.     

Characterization and diurnal variation of size-resolved inorganic water-soluble ions at a rural background site

Water-soluble inorganic ions in aerosol samples have been studied. The sample collection took place during summer in 2003 at a European background site which is operating within the framework of the European Monitoring and Evaluation Program. Gent type PM10 stacked filter unit (SFU) samplers were operated in parallel on a day and night basis to collect particles in separate coarse (2.0-10 microm) and fine (<2.0 microm) size fractions. Particulate masses were measured gravimetrically; the filters from one of the SFU samplers were analyzed by particle-induced X-ray emission spectrometry (PIXE) and instrumental neutron activation analysis (INAA). Filters from the other SFU sampler were analyzed by ion chromatography (IC) for major inorganic anions (MSA-, NO2(-), NO3(-), Cl-, Br-, SO4(2-), oxalate) and cations (Na+, K+, NH4(+), Mg2+, Ca2+). The water-soluble inorganic ions measured were responsible for 44% and 16% of the total fine and coarse particulate mass, respectively. In the fine size fraction, the main ionic components were SO4(2-) and NH4(+) accounting for about 90% of fine ionic mass. In the coarse fraction the main ionic components were Ca2+ and NO3(-), followed by SO4(2-). Significant day and night difference in the mass concentrations was observed only for fine NO3(-). The molar ratios of fine NH4(+) to SO4(2-) indicated their complete neutralization to (NH4)2SO4. According to the cation-to-anion ratios the coarse particles were alkaline, while the fine particles were slightly acidic or neutral. By comparing the corresponding concentrations obtained from PIXE/INAA and IC, we determined the water-extractable part of the individual species. We also investigated the effect of long-range transported air masses on the local air concentrations, and we found that the air quality of this background monitoring station was affected by regional pollution sources.     

A study on chemical properties of groundwater and soil in ophiolitic rocks in Firuzabad, east of Shahrood, Iran: with emphasis to heavy metal contamination

In order to assess the chemical properties of groundwater and soil in ophiolitic zone of Firuzabad, in east of Shahrood, Iran, 10 soil samples with regard to sensitive points (vicinity to mine, ophiolitic rocks, and villages) and 10 groundwater samples including nine samples from springs, and also one sample from a well in a village of the study area were taken. These samples were analyzed in laboratories using inductively coupled plasma method. The soil samples were also evaluated for grain size. The obtained results show that most of heavy and major elements were exceeding the permissible levels in soil and water samples in the study area. On the subject of soil quality, concentrations of elements Cr, Mn, Fe, Ca, Mg, Ca, Ni, and Zn are above permissible levels. Enrichment factor and index of geoaccumulation have been calculated for heavy and major elements of all soil samples. According to the obtained results, it may be argued that soil samples are contaminated in relation to the above-mentioned indices. Comparing the concentrations of elements with results of grain size analysis illustrates that the concentrations of Cr, Ni, Fe, Mg, and Co are positively correlated with sand fraction and the concentrations of Al, P, Mn, and Pb are directly proportional with clay fraction in soil samples. The study on water contamination suggests that concentrations of elements Cr, Ni, and Mg in groundwater samples of the study area are above the permissible levels. Some indices like metal index and heavy metal pollution index show that most of the water samples include heavy metal contamination.     

Reducing dust exposure in indoor climbing gyms

As users of indoor climbing gyms are exposed to high concentrations (PM(10) up to 4000 μg m(-3); PM(2.5) up to 500 μg m(-3)) of hydrated magnesium carbonate hydroxide (magnesia alba), reduction strategies have to be developed. In the present paper, the influence of the use of different kinds of magnesia alba on dust concentrations is investigated. Mass concentrations, number concentrations and size distributions of particles in indoor climbing gyms were determined with an optical particle counter, a synchronized, hybrid ambient real-time particulate monitor and an electrical aerosol spectrometer. PM(10) obtained with these three different techniques generally agreed within 25%. Seven different situations of magnesia alba usage were studied under controlled climbing activities. The use of a suspension of magnesia alba in ethanol (liquid chalk) leads to similar low mass concentrations as the prohibition of magnesia alba. Thus, liquid chalk appears to be a low-budget option to reduce dust concentrations. Magnesia alba pressed into blocks, used as powder or sieved to 2-4 mm diameter, does not lead to significant reduction of the dust concentrations. The same is true for chalk balls (powder enclosed in a sack of porous mesh material). The promotion of this kind of magnesia alba as a means of exposure reduction (as seen in many climbing gyms) is not supported by our results. Particle number concentrations are not influenced by the different kinds of magnesia alba used. The particle size distributions show that the use of magnesia alba predominantly leads to emission of particles with diameters above 1 μm.     

Carbonate induced dissolution of uranium containing precipitates under cement leachate conditions

The effects of carbonate on uranium (VI) solubility under aerobic and cementitious conditions have been investigated. The information is of relevance to low level nuclear waste disposal. Aqueous NaOH, KOH, Ca(OH)2 and a cement leachate solution were added to uranyl nitrate solution. Afterwards, increasing amounts of ammonium carbonate were added to re-dissolve the precipitates. The precipitates were characterised by means of X-ray powder diffraction (XRPD) measurements and modelling studies. The model calculations were performed using the MINTEQA2 speciation code, with an expanded database incorporating uranium stability constants taken from the HATCHES database. The measured and predicted amounts of CO3(2-) needed to dissolve the precipitates were compared. The knowledge gained from the 'pure' systems was used to rationalise the precipitation and re-dissolution behaviour observed in the leachate system. The lack of uranium solubility at low carbonate levels brought into question literature formation constants for UO2(OH)3- and UO2(OH)4(2-). An approximate log K value of 26.8 for K2U2O7 formation was estimated from the KOH results at pH 12. Generally, uranium solubilities are expected to be insignificant at low level nuclear waste sites because anaerobic conditions should persist. However, this study has demonstrated that solubility in leachate could rise at high pH and high carbonate levels, if aerobic conditions were to develop. Soluble U(VI) species would be formed. The novel part of the study has been to reproduce the effects and to correlate enhanced solubilities with model predictions. Consequently, the study has re-emphasised the need for appropriate environmental monitoring of such sites.     

Size effect on the mineralogy and chemistry of <Emphasis Type="Italic">Mytilus trossulus</Emphasis> shells from the southern Baltic Sea: implications for environmental monitoring

Mussels have the ability to control biomineral production and chemical composition, producing shells with a range of functions. In addition to biological control, the environment also seems to influence the process of biomineralization; thus, shells can be used as archives of ambient water parameters during the calcium carbonate deposition. Past and present environmental conditions are recorded in the shells in the form of various proxies including Mg/Ca or Sr/Ca ratios. For such proxies to be accurate and robust, the influence of biological effects including the size of studied organism must be examined and eliminated or minimized, so that the environmental signal can be efficiently extracted. This study considers mineralogy and elemental composition of shells representing four size classes of Mytilus trossulus from the Baltic Sea. Obtained results suggest that mineralogy and chemical composition change throughout the shell development due to most likely a combination of environmental and biological factors. The content of aragonite increases with increasing shell size, while the bulk concentrations of Na, Cd, Cu, U, V, Zn and Pb were found to decrease with increasing height of the shells. Therefore, using mussels for environmental monitoring requires analysis of individuals in the same size range.     

Comparative toxicity of nano-ZnO and bulk ZnO suspensions to zebrafish and the effects of sedimentation, ˙OH production and particle dissolution in distilled water

With the common application of nanoscale zinc oxide (nZnO) and significant potential for its release directly into aquatic environments, it is urgent to carry out research on ecotoxicological impact of nZnO. The characterization of nZnO, the amount of ˙OH in suspensions in the presence of light and the acute toxicity of nZnO and its bulk counterpart suspensions, as well as the acute toxicity of Zn(2+) solution to zebrafish (Danio rerio) at 96 h were studied. It was found that nZnO aggregated into irregular shapes in suspensions, and showed a relationship between its size distribution and concentration. In the presence of light, nZnO suspensions could generate ˙OH, the concentration of which increased with time. Although it was generally thought that ˙OH played a role in the biotoxicity to zebrafish, similar toxicity was observed for the nZnO and bulk ZnO suspensions (96 h LC(50) 3.969 mg L(-1), 2.525 mg L(-1), respectively). Furthermore, the sedimentation of nZnO and bulk ZnO in suspensions, and the accumulation of Zn in zebrafish were studied. The results showed that dissolved Zn(2+), from nZnO and bulk ZnO in suspensions, were toxic to zebrafish, while the aggregation and sedimentation of nZnO suspensions reduced the toxicity of nZnO. However, Zn(2+) may not be the main source of acute toxicity of nZnO and bulk ZnO to zebrafish. The experimental results highlight the importance of a systematic assessment of toxicity mechanisms of metal oxide nanoparticles (NPs) to determine definitively whether their toxicity is caused by nano-effects.     

Workplace aerosol mass concentration measurement using optical particle counters

Direct-reading aerosol measurement usually uses the optical properties of airborne particles to detect and measure particle concentration. In the case of occupational hygiene, mass concentration measurement is often required. Two aerosol monitoring methods are based on the principle of light scattering: optical particle counting (OPC) and photometry. The former analyses the light scattered by a single particle, the latter by a cloud of particles. Both methods need calibration to transform the quantity of scattered light detected into particle concentration. Photometers are simpler to use and can be directly calibrated to measure mass concentration. However, their response varies not only with aerosol concentration but also with particle size distribution, which frequently contributes to biased measurement. Optical particle counters directly measure the particle number concentration and particle size that allows assessment of the particle mass provided the particles are spherical and of known density. An integrating algorithm is used to calculate the mass concentration of any conventional health-related aerosol fraction. The concentrations calculated thus have been compared with simultaneous measurements by conventional gravimetric sampling to check the possibility of field OPC calibration with real workplace aerosols with a view to further monitoring particle mass concentration. Aerosol concentrations were measured in the food industry using the OPC GRIMM? 1.108 and the CIP 10-Inhalable and CIP 10-Respirable (ARELCO?) aerosol samplers while meat sausages were being brushed and coated with calcium carbonate. Previously, the original OPC inlet had been adapted to sample inhalable aerosol. A mixed aerosol of calcium carbonate and fungi spores was present in the workplace. The OPC particle-size distribution and an estimated average particle density of both aerosol components were used to calculate the mass concentration. The inhalable and respirable aerosol fractions calculated from the OPC data are closely correlated with the results of the particle size-selective sampling using the CIP 10. Furthermore, the OPC data allow calculation of the thoracic fraction of workplace aerosol (not measured by sampling), which is interesting in the presence of allergenic particles like fungi spores. The results also show that the modified COP inlet adequately samples inhalable aerosol in the range of workplace particle-size distribution.     

Application of a compact all solid-state laser system to the in situ detection of atmospheric OH,HO2, NO and IO by laser-induced fluorescence

A tuneable, high pulse-repetition-frequency, solid state Nd:YAG pumped titanium sapphire laser capable of generating radiation for the detection of OH, HO2, NO and IO radicals in the atmosphere by laser induced fluorescence (LIF) has been developed. The integration of the laser system operating at 308 nm into a field measurement apparatus for the simultaneous detection of hydroxyl and hydroperoxy radicals is described, with detection limits of 3.1 x 10(5) molecule cm(-3) (0.012 pptv in the boundary layer) and 2.6 x 10(6) molecule cm(-3) (0.09 pptv) achieved for OH and HO2 respectively (30 s signal integration, 30 s background integration, signal-to-noise ratio = 1). The system has been field tested and offers several advantages over copper vapour laser pumped dye laser systems for the detection of atmospheric OH and HO2 radicals by LIF, with benefits of greater tuning range and ease of use coupled with reduced power consumption, instrument footprint and warm-up time. NO has been detected in the atmosphere at approximately 1 ppbv by single photon LIF using the Alpha 2Sigma+ <-- Chi 2Pi1/2 (0,0) transition at 226 nm, with absolute concentrations in good agreement with simultaneous measurements made using a chemiluminescence analyser. With some improvements in performance, particularly with regard to laser power, the theoretical detection limit for NO is projected to be approximately 2 x 10(6) molecule cm(-3) (0.08 pptv). Whilst operating at 445 nm, the laser system has been used to readily detect the IO radical in the laboratory, and although it is difficult to project the sensitivity in the field, an estimate of the detection limit is < 1 x 10(5) molecule cm(-3) (< 0.004 pptv), well below previously measured atmospheric concentrations of IO.     

Aluminium in UK rivers: a need for integrated research related to kinetic factors, colloidal transport, carbon and habitat

Dissolved aluminium concentrations ([Al]) in the <0.45 μm filtered fraction are described for 54 UK river sites covering rural, acidic/acid sensitive, agricultural and urban typologies, and wide pH range (4 to 11). High [Al] occurred under acidic conditions and for acid runoff neutralised by bicarbonate rich groundwater. Thermodynamic analysis indicates Al hydroxide/hydroxy-silicate oversaturation at circumneutral pH across the rivers, but undersaturation at lower/higher pH. The oversaturation reflects in part the presence of Al bearing colloids as indicated by (1) [Al] being correlated with components associated with both lithogenic (Fe, Ti and lanthanides) colloids and organic carbon, (2) baseflow studies using cross-flow ultrafiltration and (3) comparison of our data with Acid Waters Monitoring Network (AWMN) information on labile and non-labile Al. Tree harvesting and emission reductions of SO(x) in acidic and acid sensitive catchments in mid-Wales led to acidification reversal, lower [Al] and changing [H(+)] - [Al] relationships. The [Al] decline was confined to acidic conditions while [Al] increased during the later part of the monitoring period with a peak around 2002 for moorland and forested systems. Colloidal production across the flow range was indicated late in the record by comparison of our data with information collected by the AWMN for a site in mid-Wales. This production seems interlinked with organic carbon and with dissolved CO(2) changes. In order for further understanding of Al hydrogeochemistry in river systems there is a need to integrate research that moves from equilibrium to kinetic and colloidal consideration including the critical issues of organic and inorganic controls within the context of bioavailability and aquatic stress. The colloidal Al may well be of low environmental concern to fish and other factors such as habitat may well be critical.