Adsorption of arsenate and arsenite on ferrihydrite in the presence and absence of dissolved organic carbon

The adsorption of As(V) and As(III) on synthetic two-line ferrihydrite in the presence and absence of a peat humic acid (HAp), Suwannee River fulvic acid (FA), or citric acid (CA) was investigated. Previous work with goethite has demonstrated the ability of dissolved organic carbon (DOC) to decrease As(V) and As(III) adsorption. The results obtained demonstrate that As(V) adsorption on ferrihydrite was decreased only in the presence of CA. Arsenate decreased the adsorption of all organic acids except HAp. Both FA and CA reduced As(III) adsorption on ferrihydrite, while HAp had no effect. Fulvic and citric acid adsorption on ferrihydrite was decreased in the presence of As(III); however, FA and CA adsorption increased at lower pH, which was consistent with decreased As(III) adsorption. Peat humic acid did not decrease As(III) adsorption, and we believe that the adsorption process of HAp and As(III) and As(V) on ferrihydrite are independent of each other. Previously, we observed that As(V) adsorption on goethite decreased in the presence of HAp > FA > CA, while As(III) adsorption on goethite was decreased similarly to that on ferrihydrite in the presence of CA > FA approximately HAp, yet As(III) adsorption on ferrihydrite was greater than on goethite. The observed differences between this study and the earlier study on goethite are believed to be an intricate function of ferrihydrite's surface characteristics, which affect the mechanisms of adsorption and hence the affinity of organic acids such as HAp, FA, and CA for the ferrihydrite surface. As such, the adsorption of DOCs to ferrihydrite are assumed to be less favorable and to occur with a fewer number of ligands, resulting in lower surface coverage of weaker bond strength.     

Accumulation of perchlorate in aquatic and terrestrial plants at a field scale

Previous laboratory-scale studies have documented perchlorate ClO(-)(4) uptake by different plant species, but less information is available at field scale, where ClO(-)(4) uptake may be affected by environmental conditions, such as distance to streams or shallow water tables, exposure duration, and species. This study examined uptake of ClO(-)(4) in smartweed (Polygonum spp.) and watercress (Nasturtium spp.) as well as more than forty trees, including ash (Fraxinus greggii A. Gray), chinaberry (Melia azedarach L.), elm (Ulmus parvifolia Jacq.), willow (Salix nigra Marshall), mulberry [Broussonetia papyrifera (L.) Vent.], and hackberry (Celtis laevigata Willd.) from multiple streams surrounding a perchlorate-contaminated site. Results indicate a large potential for ClO(-)(4) accumulation in aquatic and terrestrial plants, with ClO(-)(4) concentration in plant tissues approximately 100 times higher than that in bulk water. Perchlorate accumulation in leaves of terrestrial plants was also dependent on species, with hackberry, willow, and elm having a strong potential to accumulate ClO(-)(4). Generally, trees located closer to the stream had a higher ClO(-)(4) accumulation than trees located farther away from the stream. Seasonal leaf sampling of terrestrial plants indicated that ClO(-)(4) accumulation also was affected by exposure duration, with highest accumulation observed in the late growing cycle, although leaf concentrations for a given tree were highly variable. Perchlorate may be re-released into the environment via leaching and rainfall as indicated by lower perchlorate concentrations in collected leaf litter. Information obtained from this study will be helpful to understand the fate of ClO(-)(4) in macrophytes and natural systems.     

Kinetics of chromate adsorption on goethite in the presence of sorbed silicic acid

The adsorption of chromate on mineral surfaces has received much attention due to its toxicity in natural systems. Spectroscopic studies have demonstrated that chromate forms inner-sphere complexes on variable-charge surfaces. However, in natural systems chromate has been observed to be fairly mobile, which has been explained by the presence of naturally occurring ligands competing with chromate for mineral surface sites. Silicic acid is a ubiquitous ligand in soil and water environments and also sorbs strongly to variable-charge surfaces. Yet little research has examined its influence on chromate adsorption to variable-charge surfaces such as goethite. This study examined the influence of silicic acid (0.10 and 1.0 mM) on the adsorption kinetics of chromate (0.05 and 0.10 mM) on goethite over a range of common soil pH values (4, 6, and 8). The rate and total quantity of chromate adsorption decreased in all the experiments except at a pH value of 4 and a chromate concentration of 0.05 mM. The inhibition of chromate adsorption ranged from 3.1% (pH = 4, Si = 0.10 mM, chromate = 0.10 mM) to 83.3% (pH = 8, Si = 1.0 mM, chromate = 0.05 mM). The rate of chromate adsorption decreased with an increase in pH and silicic acid concentration. This was attributed to a reduction in the surface potential of goethite on silicic acid adsorption as well as a competition for surface sites. The presence of naturally occurring ligands such as silicic acid may be responsible for the enhanced mobility of chromate in natural systems and demonstrates the importance of competitive adsorption for evaluating the mobility of trace elements.     

Emissions study of co-firing waste carpet in a rotary kiln

Post-consumer carpet represents a high volume, high energy content waste stream. As a fuel for co-firing in cement kilns, waste carpet, like waste tires, has potential advantages. Technological challenges to be addressed include assessing potential emissions, in particular NO emissions (from nylon fiber carpets), and optimizing the carpet feed system. This paper addresses the former. Results of pilot-scale rotary kiln experiments demonstrate the potential for using post-consumer waste carpet as a fuel in cement kilns. Continuous feeding of shredded carpet fiber and ground carpet backing, at rates of up to 30% of total energy input, resulted in combustion without transient puffs and with almost no increase in CO and other products of incomplete combustion as compared to kiln firing natural gas only. NO emissions increased with carpet waste co-firing due to the nitrogen content of nylon fiber. In these experiments with shredded fiber and finely ground backing, carpet nitrogen conversion to NO ranged from 3 to 8%. Conversion increased with enhanced mixing of the carpet material and air during combustion. Carpet preparation and feeding method are controlling factors in fuel N conversion.     

Visible-near infrared reflectance spectroscopy for rapid, nondestructive assessment of wetland soil quality

Recent evidence supports using visible-near infrared reflectance spectroscopy (VNIRS) for sensing soil quality; advantages include low-cost, nondestructive, rapid analysis that retains high analytical accuracy for numerous soil performance measures. Research has primarily targeted agricultural applications (precision agriculture, performance diagnostics), but implications for assessing ecological systems are equally significant. Our objective was to extend chemometrics for sensing soil quality to wetlands. Hydric soils posed two challenges. First, wetland soils exhibit a wider range of organic matter concentrations, particularly in riparian areas where levels range from <1% in sedimentation zones to >90% in backwater floodplains; this may mute spectral responses from other soil fractions. Second, spectral inference of cation concentrations in terrestrial soils is for oxidized species; under reducing conditions in wetlands, oxidation state variability is observed, which strongly affects chroma. Riparian soils (n = 273) from western Florida exhibiting substantial target parameter variability were compiled. After minimal pre-processing, soils were scanned under artificial illumination using a laboratory spectrometer. A multivariate data mining technique (regression trees) was used to relate post-processed reflectance spectra to laboratory observations (pH, organic content, cation concentrations, total N, C, and P, extracellular enzyme activity). High validation accuracy was generally observed (r2(validation) > 0.8, RPD > 2.0, where RPD is the ratio of the standard deviation of an attribute to the observed standard error of validation); where accuracy was lower, categorical models (classification trees) successfully screened samples based on diagnostic functional thresholds (validation odds ratio > 10). Graphical models verified significant association between predictions and observations for all parameters, conditioning on biogeochemical covariates. Visible-near infrared reflectance spectroscopy offers both cost and statistical power advantages; hydric conditions do not appear to constrain application.     

Temporal variability in physical speciation of metals during a winter rain-on-snow event

Particulate matter in urban rivers transports a significant fraction of pollutants, changes rapidly during storm events, and is difficult to characterize. In this study, the physical speciation of trace metals and organic C in an urban river and upstream headwaters site in Torrington, CT, were measured during a winter rain-on-snow event. In addition, a selective fractionation scheme, using membrane and tangential-flow ultrafiltration methods to separate suspended particulate matter into sand, silt, clay, and colloid fractions, was evaluated based on the appropriateness of the chosen size categories. During peak runoff at the urban river site, total-recoverable concentrations of the metals Cu and Pb increased 6- and 13-fold to 16.9 and 9.5 microg L(-1), respectively, compared with baseflow concentrations. Concentrations of Cu and Pb reached only 0.9 and 0.86 microg L(-1) at the headwaters site. For the measured storm event, the majority of metals were transported by the urban river in association with coarse silt (20-80 microm particle diam.) during peak runoff. During peak runoff at the urban site, organic C associated with the large colloid fraction (0.1-1.0 microm) increased from 5% (at baseflow) to 54% of the total C in transport, whereas dissolved organic C and that associated with smaller colloids decreased from 91.5% (at baseflow) to 41% of the total. Other elements that were monitored as part of the study were Na, K, Ca, Mg, Fe, Mn, Al, Cd, Cl-, NO3(-), and SO4(2-). The chosen fractionation scheme was useful to characterize pollutant transport during this event, but further testing should be undertaken to determine the most appropriate size range categories, and to ensure that the sizes measured are comparable to those used in other studies.     

Controls on Leaching of N Species in Upland Moorland Catchments

Spatial and temporal changes in mobility of N species have been studied for three UK upland river networks, the Etherow in the South Pennines, the Nether Beck in the Lake District and the Dee in NE Scotland. The catchments are subject to N deposition at 35.1, 22.0 and 10.8–15.6 kg N ha^–1 yr^–1, respectively. TheNH ₄ ⁺ leaching appears to be predominantly regulated by flowpath in more polluted upland catchments. It is greatest where water draining acidified peaty soils contributes more to total discharge. Soluble organic matter may provide the dominant counter anion. In the Etherowand Dee catchments, which are dominated by acid mineral and organic soils, at high discharge NO ₃ ^– also appears to be associated with greater input of water from acidified soils. In contrast, for the Nether Beck, higher NO ₃ ^– concentrations are associated with tributaries draining soils contributingwater with higher alkalinity, suggesting nitrification is important. For the Etherow and Dee, dissolved organic N (DON) appears to originate predominantly from acidified, peaty soils. Spiking experiments with peat soil from the Etherow catchment confirmed the limited capacity of these soils to utilize inorganic N inputs, favouring equilibration with NH ₄ ⁺ inputs and leaching losses of inorganic N throughout the year.     

Re-evaluating energy efficiency in China

Energy efficiency is a sensible scheme for saving money, conserving natural resources and reducing CO2 emissions. However, incentives for energy conservation vary greatly between different nations. Energy prices are the key to energy conservation, many observers argue. This paper focuses on one of the world's most rapidly developing energy consumers -- China -- and contemplates the current and future impact of energy prices on China's energy-efficient behaviour.     

HYDRAULIC AND ECONOMIC BENEFITS OF DOWNSPOUT DWERSION1

ABSTRACT: A downspout diversion program in an urban area is evaluated to assess the impacts on sanitary sewer flow volumes and cost effectiveness. Sanitary sewer flows and wastewater treatment cost data are compared for the five years before and 1.25 years after the downspout diversion was completed. In order to establish a cause and effect relationship between flow volumes and downspout diversion, measurements of precipitation, consumption patterns, and system loss (maintenance, fire flows, main ruptures) for the before and after time periods were obtained. The results indicate the downspout diversion contributed to a reduction of over 25 percent in the mean flow volumes within the sanitary sewer collection network during all rainfall events, with flow reductions ranging from 25 percent to 62 percent for rainfall depths between 6 mm (0.25 inches) and 25.4 mm (1.0 inches). Costs incurred for wastewater treatment were also reduced significantly, as overtime for overflow maintenance was eliminated. Downspout diversion is a viable nonstructural alternative for sthrmwater flow reduction in highly urbanized communities which may lack available space for large scale detention facilities.     

The influence of personal protection equipment,occupant body size,and restraint system on the frontal impact responses of Hybrid III ATDs in tactical vehicles

Objective: Although advanced restraint systems, such as seat belt pretensioners and load limiters, can provide improved occupant protection in crashes, such technologies are currently not utilized in military vehicles. The design and use of military vehicles presents unique challenges to occupant safety—including differences in compartment geometry and occupant clothing and gear—that make direct application of optimal civilian restraint systems to military vehicles inappropriate. For military vehicle environments, finite element (FE) modeling can be used to assess various configurations of restraint systems and determine the optimal configuration that minimizes injury risk to the occupant. The models must, however, be validated against physical tests before implementation. The objective of this study was therefore to provide the data necessary for FE model validation by conducting sled tests using anthropomorphic test devices (ATDs). A secondary objective of this test series was to examine the influence of occupant body size (5th percentile female, 50th percentile male, and 95th percentile male), military gear (helmet/vest/tactical assault panels), seat belt type (3-point and 5-point), and advanced seat belt technologies (pretensioner and load limiter) on occupant kinematics and injury risk in frontal crashes.

Methods: In total, 20 frontal sled tests were conducted using a custom sled buck that was reconfigurable to represent both the driver and passenger compartments of a light tactical military vehicle. Tests were performed at a delta-V of 30 mph and a peak acceleration of 25 g. The sled tests used the Hybrid III 5th percentile female, 50th percentile male, and 95th percentile male ATDs outfitted with standard combat boots and advanced combat helmets. In some tests, the ATDs were outfitted with additional military gear, which included an improved outer tactical vest (IOTV), IOTV and squad automatic weapon (SAW) gunner with a tactical assault panel (TAP), or IOTV and rifleman with TAP. ATD kinematics and injury outcomes were determined for each test.

Results: Maximum excursions were generally greater in the 95th percentile male compared to the 50th percentile male ATD and in ATDs wearing TAP compared to ATDs without TAP. Pretensioners and load limiters were effective in decreasing excursions and injury measures, even when the ATD was outfitted in military gear.

Conclusions: ATD injury response and kinematics are influenced by the size of the ATD, military gear, and restraint system. This study has provided important data for validating FE models of military occupants, which can be used for design optimization of military vehicle restraint systems.