Isotopic characterisation of lead deposited 1989-2001 at two upland Scottish locations

The isotopic composition of lead collected with grass samples taken over the period 1989-2001 from plots at two upland locations (Glensaugh in north east and Hartwood in central Scotland) has been determined using thermal ionisation mass spectrometry. Although marked reductions in lead concentrations in grass were observed at Glensaugh in the initial three years, subsequently concentrations have remained relatively constant (1-3 microg g(-1)) in all plots to the present day. The one exception was a roadside plot at Hartwood which showed a large reduction from 1.0 microg g(-1) in 1999 to 0.2 microg g(-1) in 2000 following the abolition of petrol lead in the UK at the beginning of 2000. The total concentrations at this plot were consistently lower than those found at plots away from road traffic but exposed to the prevailing wind direction. The 206Pb/207Pb ratio increased steadily at all the plots throughout the period of the study indicating the reducing influence of petrol lead but the changes were not as great as might be expected with the decrease in the use of leaded petrol. Assuming the collected lead had only two sources, petrol lead and a diffuse background "industrial" lead, the proportion of petrol lead was only in the range 17-69% for roadside samples and 0-39% in other samples. A substantial proportion of deposited lead, therefore, now has its origin other than in petrol. Mixing curves indicate that whereas the lead deposited at Glensaugh could be defined by only two end members, that at Hartwood needs more than two components in the mixture. The results also suggest that although petrol lead has been eliminated, traffic is still a source of lead and another source defined as "traffic lead" should be considered.     

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.     

Distribution of Chlorinated Organic Pollutants in Harbor Sediments of Livorno (Italy): A Multivariate Approach to Evaluate Dredging Sediments

Dredging is a very important procedure for harbor management. InItaly the guidelines for the offshore dumping of dredged materials are issued by the Ministry of Environment. Theydescribed a few steps of dredging activities, such as thesampling strategy, but do not deal with limits or guide-valuesfor the chemical, physical and biological composition of theresulting sediments. The quality of dredged materials is mainlydependent on the presence of inorganic and organic pollutants.In particular, polychlorinated biphenyls (PCBs) and organo-chlorinated pesticides are seen as a high priority inmarine environment by international organizations because oftheir persistence, toxicity and bioaccumulation capacity.In this article the presence of some PCBs and organo-chlorinatedpesticides in sediment samples collected from the harbor ofLivorno (Northern Tyrrhenian Sea) was investigated. Theconcentration of HCHs, Aldrin, Chlordanes, DDEs, DDTs, and PCBsin 12 representative sites ranged between <1 g kg^–1and 95, 19, 32, 35, 107, and 111 g kg^–1, respectively.The application of univariate and multivariate statisticaltechniques, such as linear regression analysis and principalcomponent analysis, to the experimental data showed a differentdistribution of PCBs in the two sediment layers. On thecontrary, the vertical distribution of the other investigatedpollutants was more homogeneous and affected by randomvariability. The multivariate approach was an important tool to establish more rational criteria for the management of dredged materials.     

Preliminary air pollution monitoring in San Miguel, Buenos Aires

Passive diffusion samplers were employed in San Miguel(Buenos Aires Metropolitan Area) for a preliminary airpollution monitoring. The highest loads were observedin downtown, compared with an urban background site.Total suspended particulate matter (TSPM) varied from0.257 to 0.033 mg cm^-2 month^-1; dust was examinedfor particle nature and size distribution. A similartrend was observed for nitrogen dioxide (NO₂) andTSPM spatial distribution, suggesting that traffic isthe major pollution source. Sulphur dioxide (SO₂)values were low and rather homogeneous. Levels for theinvestigated pollutants are below EPA's guide linevalues. Geographic (flat area, near to Rio de LaPlata) and climatologic factors (rainfalls andvariable wind directions) contribute to disperse pollutants.     

Application of intrawell testing of RCRA groundwater monitoring data when no upgradient well exists

A statistical quality control approachto detect changes in groundwater quality from aregulated waste unit is described. The approachapplies the combined Shewhart-CUSUM control chartmethodology for intrawell comparison of analyteconcentrations over time and does not require anupgradient well. A case study from the U.S.Department of Energy's Hanford Site is used forillustration purposes. This method is broadlyapplicable in groundwater monitoring programs wherethere is no clearly defined upgradient location, thegroundwater flow rate is exceptionally slow, or wherea high degree of spatial variability exists inparameter concentrations. This study also indicatesthat the use of the Data Quality Objectives (DQO)process can assist in designing an efficient andcost-effective groundwater monitoring plan to achievethe optimum goal of both low false positive and lowfalse negative rates (high power).     

A Watershed-based Cumulative Risk Impact Analysis: Environmental Vulnerability and Impact Criteria

Swine Concentrated Animal Feeding Operations (CAFOs) have received much attention in recent years. As a result, a watershed-based screening tool, the Cumulative Risk Index Analysis (CRIA), was developed to assess the cumulative impacts of multiple CAFO facilities in a watershedsubunit. The CRIA formula calculates an index number based on: 1) the area of one or more facilities compared to the area of the watershed subunit, 2) the average of the environmental vulnerability criteria, and 3) the average of the industry-specific impact criteria. Each vulnerability or impact criterion is ranked on a 1 to 5 scale, with a low rank indicating low environmental vulnerability or impact and a high rank indicating high environmental vulnerability or impact. The individual criterion ranks, as well as the total CRIA score, can be used to focus the environmental analysis and facilitate discussions with industry, public, and other stakeholders in the Agency decision-making process.     

Measurements of fractionated gaseous mercury concentrations over northwestern and central Europe, 1995-99

Although it makes up only a few per cent. of total gaseous mercury (TGM) in the atmosphere, the fraction of oxidised (divalent) mercury plays a major role in the biogeochemical cycle of mercury due to its high affinity for water and surfaces. Quantitative knowledge of this fraction present in mixing ratios in the parts-per-10(15) (ppq) range is currently very scarce. This work is based on approximately 220 data for divalent gaseous mercury (DGM) collected during 1995-99 in ambient air. Over the course of the measurements, the sampling and analytical methods were modified and improved. This is described here in detail and includes transition from wet leaching and reduction procedures to thermo-reductive desorption, the use of annular as well as tubular denuders and adoption of an automated sampling system. The concentration of DGM exhibited a strong seasonal behaviour in contrast to atomic gaseous mercury, with low values in winter and maximum values in summer. The DGM/TGM ratios were frequently found to be below the detection limit (< or = 1%) and in the range 1-5%. A trend of diurnal DGM patterns was observed and implies photolytically induced sources. Scavenging of DGM during rain events was also noticed.     

Collaborative study to improve the quality control of rare earth element determinations in environmental matrices

In order to control the quality of rare earth determinations in environmental matrices, the Standards, Measurements and Testing Programme (formerly Community Bureau of Reference, BCR) of the European Commission has started a project, the final aim of which is to certify four types of matrices (tuna muscle, mussel tissue, aquatic plant and estuarine sediment) for their contents of a range of rare earth elements (Sc, Y and the lanthanides: La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu). The elements U and Th were added to the study. The first part of this project consisted of an interlaboratory study which aimed to test the feasibility of preparation of environmental reference materials and to detect and remove most of the pitfalls observed in rare earth determinations. This paper presents the preparation of the four matrices for the intercomparison study and for the candidate reference material. The main results are presented of the interlaboratory study that was carried out prior to the certification campaign. This collaborative trial is the first attempt ever carried out at this scale to evaluate the state-of-the-art of rare earth determinations in the environment. Its impact on the improvement of chemical measurements will have positive effects on the comparability of data necessary for environmental monitoring.     

Evaluation of two adsorbents for diffusive sampling and thermal desorption-gas chromatographic analysis of monoterpenes in air

Tube type samplers with two different adsorbents, Chromosorb 106 and Tenax TA, were evaluated by laboratory experiments and field tests for simultaneous diffusive sampling of alpha-pinene, beta-pinene and delta 3-carene and subsequent thermal desorption-gas chromatographic analysis. No statistically significant effects of exposure time, concentrations of monoterpenes or relative humidity were found for samplers with Chromosorb 106 when running a factorial design, with the exception of the adsorption of delta 3-carene, for which some weak effects were noted. Samplers with Tenax TA were affected by the sampling time as well as the concentration for all terpenes, with a strong interaction effect between these two factors. The terpenes showed good storage stability on both adsorbents. No effect of back-diffusion was noted when using Chromosorb 106, while Tenax TA showed some back-diffusion effects. The uptake rates, in ml min-1, for the terpenes on Chromosorb 106 were 0.36 for alpha-pinene, 0.36 for beta-pinene and 0.40 for delta 3-carene. The corresponding average values on Tenax TA were 0.30 for alpha-pinene, 0.32 for beta-pinene and 0.38 for delta 3-carene. The field validation proved that diffusive sampling on Chromosorb 106 agreed well with pumped sampling on charcoal for stationary samples, while the personal samples indicated a discrepancy of 25% between Chromosorb 106 and charcoal samples. Tenax TA generally gave lower results than Chromosorb 106 in all field samples. Samplers packed with Chromosorb 106 could be used to monitor terpene levels in workplaces such as sawmills. The major advantages with this method are the sampling procedure, which is simple to perform compared to other techniques, the easily automated analysis procedure and the possibility to reuse the samplers.