Arsenic mobilization and attenuation by mineral-water interactions: implications for managed aquifer recharge

Managed aquifer recharge (MAR) has potential for addressing deficits in water supplies worldwide. It is also widely used for preventing saltwater intrusion, maintaining the groundwater table, and augmenting ecological stream flows, among many other beneficial environmental applications. However, field MAR sites have experienced arsenic mobilization from aquifer formation minerals due to induced changes in groundwater chemistry. To address this environmental concern, it is crucial to understand the potential sources and sinks impacting arsenic mobilization. This paper outlines important mineral-water interactions that can occur at MAR sites. Detailed information on minerals of concern, physiochemical processes for arsenic mobilization or attenuation, and the potential impact of microbial activity and hydrology on these processes is provided. Based on these mineral-water interactions, guidelines for predicting arsenic mobility are presented, and recommendations are made concerning MAR site monitoring. The review emphasizes important aspects in correlating interfacial reactions to reactive transport modeling and elucidating future challenges, a first step toward developing safer and more sustainable MAR operations.     

A statistical F test for the natural attenuation of contaminants in groundwater

Natural attenuation (NA) is a catchall explanation for the overall decay and slowed movement of the contaminants in the subsurface. One direct support to NA is to demonstrate that contaminant concentrations from monitoring wells located near the source are decreasing over time. The decrease is summarily expressed in terms of an apparent half-life that is determinedfrom the line best fitting the observed log-transformed concentration data and time. This simple (time-only) decay modelassumes other factors are invariant, and so is flawed when complicating factors – such as a fluctuating water table – are present. A history of the water-table fluctuation can track changes in important NA factors like recharge, groundwater flow direction and velocity, as well as other non-NA factors like volume of water in and purged from the well before a sample is collected. When the trend in the concentrations is better associated with the water table rising or falling, any conclusionabout degradation rate may be premature. We develop simple regressions to predict contaminant concentration (c) by two line models: one involving time (c c(t)), and another involving groundwater elevation (c c(z)). We develop a third model that includesboth factors (c c(t, z)). Using an F-test to compare the fits to the models, we determine which modelis statistically better in explaining the observed concentrations. We applied the test to sites where benzene degradation rates had previously been estimated. The F-testcan be used to determine the suitability of applying non-parametric statistics, like the Mann-Kendall, to the concentration data, because the result from the F-test canindicate instability of the contaminant plume that may bemasked when the water table fluctuates.     

Characterisation of weathered hydrocarbon wastes at contaminated sites by GC-simulated distillation and nitrous oxide chemical ionisation GC-MS, with implications for bioremediation

An extended analytical characterisation of weathered hydrocarbons isolated from historically contaminated sites in Alberta is presented. The characterisation of soil extracts, chromatographically separated into component classes, by GC-simulated distillation and nitrous oxide (N2O) chemical ionisation (CI) GC-MS provides new insights into the composition of the residual oil at these sites, the principal partition medium for risk critical components. The combined polar and asphaltene content of representative soil extracts ranged from 40% w/w to 70% w/w of the oils encountered. An abundance of C14-C22 2-4 ring alicyclics, alkylbenzenes and benzocycloparaffins is prevalent within the saturate fractions of site soils. Implications for the partitioning of risk critical compounds at sites with weathered hydrocarbons and the practical application of bioremediation technologies are discussed.     

The estimation and interpretation of air quality trends,including some implications for network design

A review is given of methods being used to identify and interpret trends in air quality data from single stations and from networks of stations. Some comments are also included concerning the problem of designing networks which will identify trends as quickly as possible, thus providing early warnings of significant changes in air quality.Reprinted from the Preprint Volume, WMO Technical Conference on Regional and Global Observation of Atmospheric Pollution Relative to Climate, Boulder, Col., Aug. 1979, WMO Geneva, No. 549.     

Soil and vegetation carbon stocks in Brazilian Western Amazonia: relationships and ecological implications for natural landscapes

The relationships between soils attributes, soil carbon stocks and vegetation carbon stocks are poorly know in Amazonia, even at regional scale. In this paper, we used the large and reliable soil database from Western Amazonia obtained from the RADAMBRASIL project and recent estimates of vegetation biomass to investigate some environmental relationships, quantifying C stocks of intact ecosystem in Western Amazonia. The results allowed separating the western Amazonia into 6 sectors, called pedo-zones: Roraima, Rio Negro Basin, Tertiary Plateaux of the Amazon, Javari-Juruá-Purus lowland, Acre Basin and Rondonia uplands. The highest C stock for the whole soil is observed in the Acre and in the Rio Negro sectors. In the former, this is due to the high nutrient status and high clay activity, whereas in the latter, it is attributed to a downward carbon movement attributed to widespread podzolization and arenization, forming spodic horizons. The youthful nature of shallow soils of the Javari-Juruá-Purus lowlands, associated with high Al, results in a high phytomass C/soil C ratio. A similar trend was observed for the shallow soils from the Roraima and Rondonia highlands. A consistent east–west decline in biomass carbon in the Rio Negro Basin sector is associated with increasing rainfall and higher sand amounts. It is related to lesser C protection and greater C loss of sandy soils, subjected to active chemical leaching and widespread podzolization. Also, these soils possess lower cation exchangeable capacity and lower water retention capacity. Zones where deeply weathered Latosols dominate have a overall pattern of high C sequestration, and greater than the shallower soils from the upper Amazon, west of Madeira and Negro rivers. This was attributed to deeper incorporation of carbon in these clayey and highly pedo-bioturbated soils. The results highlight the urgent need for refining soil data at an appropriate scale for C stocks calculations purposes in Amazonia. There is a risk of misinterpreting C stocks in Amazonia when such great pedological variability is not taken into account.     

Nutrient baselines of Cerrado low-order streams: comparing natural and impacted sites in Central Brazil

The aquatic systems responsible for water supply in the Brazilian Federal District (FD) have been threatened by anthropogenic pressures, especially considering the expressive demographic increase in the region during the last decades. The purposes of this research were: (a) to assess the water quality in streams located in the FD by monitoring physical–chemical variables; (b) to define baselines for these variables among different ecological status categories. The 14 investigated streams were sampled between 2006 and 2009, in the dry (August–September, 2006, 2008, 2009) and rainy (March–April, 2008, 2009) seasons. All sampling sites were classified in four categories (“very impacted”, “impacted”, “in transition” and “natural”) using an adaptation of a rapid habitat assessment protocol. Differences in water quality among sites were generally well predicted in the four ecological status categories defined by the protocol, which showed a gradient in nutrient concentrations from reference sites classified as “natural” (medians: electrical conductivity?=?7.3 μS cm^?1; nitrate?=?0.040 mg L^?1; ammonium?=?0.039 mg L^?1; soluble reactive phosphorus (SRP)?=?<0.001 mg L^?1; total phosphorus (TP)?=?0.006 mg L^?1; ) to those classified as “very impacted” (medians: electrical conductivity?=?87.7 μS cm^?1; nitrate?=?0.247 mg L^?1; ammonium?=?0.219 mg L^?1; SRP?=?0.010 mg L^?1; TP?=?0.035 mg L^?1). Point sources inputs were the main factor for water quality deterioration. The nutrient baselines reported were relatively low when compared to data collected from reference areas in Brazil (e.g., São Paulo State) or temperate regions, especially for TP.     

Comparison of elemental and black carbon measurements during normal and heavy haze periods: implications for research

Studies specifically addressing the elemental carbon (EC)/black carbon (BC) relationship during the transition from clean-normal (CN) air quality to heavy haze (HH) are rare but have important health and climate implications. The present study, in which EC levels are measured using a thermal-optical method and BC levels are measured using an optical method (aethalometer), provides a preliminary insight into this issue. The average daily EC concentration was 3.08?±?1.10 μg/m³ during the CN stage but climbed to 11.77?±?2.01 μg/m³ during the HH stage. More importantly, the BC/EC ratio averaged 0.92?±?0.14 during the CN state and increased to 1.88?±?0.30 during the HH state. This significant increase in BC/EC ratio has been confirmed to result partially from an increase in the in situ light absorption efficiency (σ _ap) due to an enhanced internal mixing of the EC with other species. However, the exact enhancement of σ _ap was unavailable because our monitoring scheme could not acquire the in situ absorption (b _ap) essential for σ _ap calculation. This reveals a need to perform simultaneous measurement of EC and b _ap over a time period that includes both the CN and HH stages. In addition, the sensitivity of EC to both anthropogenic emissions and HH conditions implies a need to systematically study how to include EC complex (EC concentration, OC/EC ratio, and σ _ap) as an indicator in air quality observations, in alert systems that assess air quality, and in the governance of emissions and human behaviors.     

Assessment of natural radiation exposure levels and mass attenuation coefficients of lime and gypsum samples used in Turkey

The activity concentrations of ²²⁶Ra, ²³²Th, and ⁴⁰K in lime and gypsum samples used as building materials in Turkey were measured using gamma spectrometry. The mean activity concentrations of ²²⁶Ra, ²³²Th, and ⁴⁰K were found to be 38 ± 16, 20 ± 9, and 156 ± 54 Bq kg^???1 for lime and found to be 17 ± 6, 13 ± 5, and 429 ± 24 Bq kg^???1 for gypsum, respectively. The radiological hazards due to the natural radioactivity in the samples were inferred from calculations of radium equivalent activities (Ra_eq), indoor absorbed dose rate in the air, the annual effective dose, and gamma and alpha indices. These radiological parameters were evaluated and compared with the internationally recommended limits. The experimental mass attenuation coefficients (μ/ρ) of the samples were determined in the energy range 81–1,332 keV. The experimental mass attenuation coefficients were compared with theoretical values obtained using XCOM. It is found that the calculated values and the experimental results are in good agreement.     

A risk-based screening approach for prioritizing contaminants and exposure pathways at Superfund sites

Contamination at Superfund sites can involve mixtures of chemicals and radionuclides in a variety of environmental media. Determining priorities for evaluation and remediation of various contaminants is an important part of the initial phases of any site investigation. An effective screening analysis at the beginning of the project can help by identifying both those situations in need of immediate remedial attention and those which require further sampling and evaluation. The screening approach discussed here is made up of two sets of calculations designed to provide upper- and lower-bound estimates of health risk to individuals likely to receive the highest exposures. This approach allows rapid identification of contaminants which pose a negligible risk and can be assigned a low priority for remedial attention or which pose a substantial risk and should be given the highest priority for appropriate remediation efforts. Contaminants designated as neither high- nor low-priority should be investigated in more detail prior to making decisions regarding the need for or method of remediation. The utility of this approach has already been demonstrated in the evaluation of contamination in the Clinch and Tennessee River systems originating from historical operations of atomic weapons and energy research facilities near Oak Ridge, Tennessee.     

Occurrence and removal of titanium at full scale wastewater treatment plants: implications for TiO2 nanomaterials

Titanium dioxide nanoparticles increasingly will be used in commercial products and have a high likelihood of entering municipal sewage that flows to centralized wastewater treatment plants (WWTPs). Treated water (effluent) from WWTPs flows into rivers and lakes where nanoparticles may pose an ecological risk. To provide exposure data for risk assessment, titanium concentrations in raw sewage and treated effluent were determined for 10 representative WWTPs that use a range of unit processes. Raw sewage titanium concentrations ranged from 181 to 1233 μg L(-1) (median of 26 samples was 321 μg L(-1)). The WWTPs removed more than 96% of the influent titanium, and all WWTPs had effluent titanium concentrations of less than 25 μg L(-1). To characterize the morphology and presence of titanium oxide nanoparticles in the effluent, colloidal materials were isolated via rota-evaporation, dialysis and lyophilization. High resolution transmission electron microscopy and energy dispersive X-ray analysis indicated the presence of spherical titanium oxide nanoparticles (crystalline and amorphous) on the order of 4 to 30 nm in diameter in WWTP effluents. This research provides clear evidence that some nanoscale particles will pass through WWTPs and enter aquatic systems and offers a methodological framework for collecting and analyzing titanium-based nanomaterials in complex wastewater matrices.     

Spatial contaminant heterogeneity: quantification with scale of measurement at contrasting sites

Material within the terrestrial environment is rarely homogeneously distributed, either spatially or temporally. One consequence of heterogeneity is that uncertainty is usually generated in measurements that are taken with the aim of characterising the environment. For example, a measurement of analyte concentration within soil taken from one sampling location on contaminated land can vary substantially when compared against another sample taken at effectively the same nominal location. The measurement uncertainty arising from the heterogeneity can substantially limit the reliability of the interpretations made upon environmental investigations. The sampling uncertainty usually outweighs the analytical uncertainty from the laboratory, often by a factor of 20 or more. One approach to reducing the uncertainty is to design a more suitable sampling strategy. This might be achieved by predicting the degree of heterogeneity prior to the investigation, but this is often difficult to achieve accurately. Another approach, which was investigated here, is to actually characterise the heterogeneity prior to the main investigation using rapid and inexpensive technology, such as in situ measurement techniques. In situ portable X-ray fluorescence (PXRF) and X-ray microprobe (XMP) techniques were employed to test the feasibility of this approach. Two contrasting contaminated land sites were chosen to characterise the two-dimensional spatial heterogeneity of heavy metal contamination in topsoil at a range of scales (50 m to 0.001 m). The spatial heterogeneity of contaminants, expressed as relative standard deviations, was found to differ between the two sites by a factor of two, largely due to the mode of deposition of pollution. The study also indicated that the heterogeneity did not change systematically with the scale of measurement between sampling locations at either site.     

Decision support methods for the environmental assessment of contamination at mining sites

Polluting mine accidents and widespread environmental contamination associated with historic mining in Europe and elsewhere has triggered the improvement of related environmental legislation and of the environmental assessment and management methods for the mining industry. Mining has some unique features such as natural background pollution associated with natural mineral deposits, industrial activities and contamination located in the three-dimensional sub-surface space, the problem of long-term remediation after mine closure, problem of secondary contaminated areas around mine sites and abandoned mines in historic regions like Europe. These mining-specific problems require special tools to address the complexity of the environmental problems of mining-related contamination. The objective of this paper is to review and evaluate some of the decision support methods that have been developed and applied to mining contamination. In this paper, only those methods that are both efficient decision support tools and provide a ‘holistic’ approach to the complex problem as well are considered. These tools are (1) landscape ecology, (2) industrial ecology, (3) landscape geochemistry, (4) geo-environmental models, (5) environmental impact assessment, (6) environmental risk assessment, (7) material flow analysis and (8) life cycle assessment. This unique inter-disciplinary study should enable both the researcher and the practitioner to obtain broad view on the state-of-the-art of decision support methods for the environmental assessment of contamination at mine sites. Documented examples and abundant references are also provided.     

A GIS-based approach for the long-term prediction of human health risks at contaminated sites

A Health Index/Risk Evaluation Tool (HIRET) has been developed for the integration of risk assessment and spatial planning using GIS capabilities. The method is meant to assist decision makers and site owners in the evaluation of potential human health risk with respect to land use. Human health risk defined as the potential adverse effects on human life or health is generally accepted as the most important aspect for site assessment and planning of remediation strategies. It concerns polluted sites that endanger human health on one hand and derelict land that does not cause the immediate risk on the other hand. In current state-of-the-art risk-assessment, long-term spatial and temporal changes of risks, in relation to changes in contamination patterns and land use functions, are not taken into account. The aim of this paper is to demonstrate the methodology developed for human health risk assessment in aspect of spatial and temporal domain. HIRET was developed as an extension for ESRI software ArcView 3.2 and allows performing dynamic human health risk assessment in long-term period, which is relevant for land use planning. The paper illustrates how such methodology can assist in environmental decision-making to enhance the efficiency of contaminated land management. A case study of contaminated site is given showing how data can be used within a GIS framework to produce maps indicating areas of potential human health risk.     

Comparison study of five analytical methods for the fractionation and subsequent determination of aluminium in natural water samples

Five methods for aluminium fractionation used in different laboratories in Norway and Finland were compared using six control, 75 soil water and 10 lake water samples. Different fractionation principles [cation exchange, formation of the Pyrocatechol Violet (PCV) or quinolin-8-ol (oxine) complex], types of cation exchanger [Amberlite (Na/H) or Bond Elut (H)], reaction time (from 2.3 s), flow systems (flow injection analysis or segmented flow) and determination principles (molecular absorption spectrometry or ICP-AES) were tested. Determination of the 'labile' fraction was strongly dependent on the method used and the largest differences were observed between the ICP-AES method with cation exchange (Bond Elut H form) and the 'quickly reacting' method (oxine, 2.3 s). Different flow systems, both using cation exchange and determination of the PCV complex but with different reaction times and an extra acidification step, resulted in large differences in the 'reactive' and 'non-labile' fractions determined. However, the determination of the labile fraction gave similar results with both these methods. The two different types of cation exchanger used (with and without pH buffering and with different counter ions) in the ICP-AES methods resulted in differences, mainly because of a smaller 'non-labile' fraction in the non-buffered system. The two flow injection systems (oxine and PCV complexation) showed common trends, which may be connected with the short reaction times used. Comparison with theoretical equilibrium calculations using the model ALCHEMI suggested that the best correlation for the determination of the 'labile' fraction were obtained with the ICP-AES method with an Amberlite column.     

Measurements of stem diameter: implications for individual- and stand-level errors

Stem diameter is one of the most common measurements made to assess the growth of woody vegetation, and the commercial and environmental benefits that it provides (e.g. wood or biomass products, carbon sequestration, landscape remediation). Yet inconsistency in its measurement is a continuing source of error in estimates of stand-scale measures such as basal area, biomass, and volume. Here we assessed errors in stem diameter measurement through repeated measurements of individual trees and shrubs of varying size and form (i.e. single- and multi-stemmed) across a range of contrasting stands, from complex mixed-species plantings to commercial single-species plantations. We compared a standard diameter tape with a Stepped Diameter Gauge (SDG) for time efficiency and measurement error. Measurement errors in diameter were slightly (but significantly) influenced by size and form of the tree or shrub, and stem height at which the measurement was made. Compared to standard tape measurement, the mean systematic error with SDG measurement was only ?0.17 cm, but varied between ?0.10 and ?0.52 cm. Similarly, random error was relatively large, with standard deviations (and percentage coefficients of variation) averaging only 0.36 cm (and 3.8%), but varying between 0.14 and 0.61 cm (and 1.9 and 7.1%). However, at the stand scale, sampling errors (i.e. how well individual trees or shrubs selected for measurement of diameter represented the true stand population in terms of the average and distribution of diameter) generally had at least a tenfold greater influence on random errors in basal area estimates than errors in diameter measurements. This supports the use of diameter measurement tools that have high efficiency, such as the SDG. Use of the SDG almost halved the time required for measurements compared to the diameter tape. Based on these findings, recommendations include the following: (i) use of a tape to maximise accuracy when developing allometric models, or when monitoring relatively small changes in permanent sample plots (e.g. National Forest Inventories), noting that care is required in irregular-shaped, large-single-stemmed individuals, and (ii) use of a SDG to maximise efficiency when using inventory methods to assess basal area, and hence biomass or wood volume, at the stand scale (i.e. in studies of impacts of management or site quality) where there are budgetary constraints, noting the importance of sufficient sample sizes to ensure that the population sampled represents the true population.     

Seasonal variation for the ratio of BaP to BeP at different sites in Great Xiamen Bay

From March 2008 to February 2009, PM(10) samples were collected and analyzed for polycyclic aromatic hydrocarbons (PAHs) at eight sampling sites in Great Xiamen Bay, China. Analyses of the seasonal and spatial variations of these compounds revealed the following results. Significantly high levels of PAHs were found in the winter compared to the summer, sometimes exceeding 100 ng m(-3), and the spatial variations were influenced most by the sampling site surroundings. Composition profiles of PAHs of an urban and a rural site were shown to be very similar with a positive correlation coefficient larger than 0.9 at the 0.01 level of significance for the same season. Diagnostic ratios, together with principal component and multiple linear regression analysis, showed that more PAHs were from grass/wood/coal combustion in winter than in other seasons. The ratios of benzo[a]pyrene to benzo[e]pyrene (BaP-BeP) in winter and fall were 0.6-1.7 times higher than those in spring and summer, suggesting the importance of local emissions of PAHs. The BaP-BeP ratios in Kinmen were generally lower than those in Xiamen, indicating that the aging degree of PAHs was higher in Kinmen than in Xiamen. The external input of PAHs from upwind urban and industrial areas was one of the key factors causing high levels of PAHs in PM(10) in Great Xiamen Bay in winter.     

Atmospheric ambient trace element concentrations of PM10 at urban and sub-urban sites: source apportionment and health risk estimation

In this study, PM₁₀ concentrations and elemental (Al, Fe, Sc, V, Cr, Mn, Co, Ni, Cu, Zn, As, Se, Mo, Ag, Cd, Sn, Sb, Ba, Pb, and Bi) contents of particles were determined in Düzce, Turkey. The particulate matter samplings were carried out in the winter and summer seasons simultaneously in both urban and sub-urban sampling sites. The average PM₁₀ concentration measured in the winter season was 86.4 and 27.3 μg/m³, respectively, in the urban and sub-urban sampling sites, while it was measured as 53.2 and 34.7 μg/m³ in the summer season. According to the results, it was observed that the PM₁₀ levels and the element concentrations reached higher levels, especially at the urban sampling site, in the winter season. The positive matrix factorization model (PMF) was applied to the data set for source apportionment. Analysis with the PMF model revealed six factors for both the urban (coal combustion, traffic, oil combustion, industry, biomass combustion, and soil) and sub-urban (industry, oil combustion, traffic, road dust, soil resuspension, domestic heating) sampling sites. Loadings of grouped elements on these factors showed that the major sources of the elements in the atmosphere of Düzce were traffic, fossil fuel combustion, and metal industry-related emissions.     

Comparison of dissolved organic matter fractions in a secondary effluent and a natural water

This research compared the structural and chemical characteristics among dissolved organic matter (DOM) fractions within the same source and among different origins. Samples taken from the Taiping Wastewater Treatment Plant (TWTP) (Harbin, China) and from the Songhuajing River (SR), Heilongjiang Province, China were chosen to represent waters containing DOM of wastewater origin and of natural-water origin, respectively. DOM was fractionated using XAD resins into five fractions: hydrophobic acid (HPO-A), hydrophobic neutral (HPO-N), transphilic acid (TPI-A), transphilic neutral (TPI-N) and hydrophilic fraction (HPI). The SR fractions were more UV-sensitive and more reactive with chlorine in formation of trihalomethanes (THMs) than the TWTP secondary effluent (TSE) fractions. The aromatic character peaks in the Fourier-transform infrared (FT-IR) spectra of SR fractions were clearer than those of TSE fractions. On the other hand, the peaks of carbohydrates in TSE fractions were more prominent in comparison with SR fractions. In addition, the amide-2 peak was present in the spectra of all the five TSE fractions but not visible in the spectra of SR fractions. The fluorescence results showed that SR DOM fractions contained more fulvic acid-like fluorescent compounds while TSE DOM fractions had higher amounts of protein-like fluorescent components.     

Comparison of two dynamic measurement methods of odor and odorant emission rates from freshly dewatered biosolids

Odor and odorant emission rates from freshly dewatered biosolids in a dewatering building of a Water Reclamation Plant (WRP) are measured using the EPA flux chamber and wind tunnel methods. Experimental results are compared statistically to test whether the two methods result in similar emission rates when experiments are performed under field conditions. To the best of our knowledge the literature is void of studies comparing the two methods indoors. In this paper the two methods are compared indoors where the wind velocity and air exchange rate are pertinent field conditions and can be measured. The difference between emission rates of odor and hydrogen sulfide measured with the two methods is not statistically significant (P values: 0.505 for odor, 0.130 for H(2)S). It is concluded that both methods can be used to estimate source emissions but selection of the most effective or efficient method depends on prevailing environmental conditions. The wind tunnel is appropriate for outdoor environments where wind effects on source emissions are more pronounced than indoors. The EPA flux chamber depends on the air exchange rate of the chamber, which simulates corresponding conditions of the indoor environment under investigation and is recommended for estimation of indoor pollution sources.