Speciation/fractionation of nickel in airborne particulate matter: improvements in the Zatka sequential leaching procedure

Modifications are reported to the sequential leaching analytical method for nickel speciation/fractionation specified by Zatka so that larger sample masses can be analyzed. Improvements have been made in the completeness of the sulfide/metallic separation during the peroxide-citrate leach step by use of a larger volume of leachant, a longer leach duration and an orbital shaker. Minimal extraction of metallic nickel in this prolonged sulfidic nickel extraction has been confirmed. An increase in the number of samples analyzed simultaneously using these modifications has resulted in substantial productivity improvements and concomitant lower costs. It is critical for practitioners of sequential leaching techniques to recognize potential limitations and to use professional judgment when interpreting results. For example, results obtained may not be biologically relevant in assessing health risks; the acts of sampling and storage may result in changes in fractionation with time; surface coatings/films may alter the ability of a leachant to react with the target compound; and leaching behaviours may be different for samples differing only in particle size distributions.     

Ecological Responses to Trout Habitat Rehabilitation in a Northern Michigan Stream

Monitoring of stream restoration projects is often limited and success often focuses on a single taxon (e.g., salmonids), even though other aspects of stream structure and function may also respond to restoration activities. The Ottawa National Forest (ONF), Michigan, conducted a site-specific trout habitat improvement to enhance the trout fishery in Cook’s Run, a 3^rd-order stream that the ONF determined was negatively affected by past logging. Our objectives were to determine if the habitat improvement increased trout abundances and enhanced other ecological variables (overall habitat quality, organic matter retention, seston concentration, periphyton abundance, sediment organic matter content, and macroinvertebrate abundance and diversity) following rehabilitation. The addition of skybooms (underbank cover structures) and k-dams (pool-creating structures) increased the relative abundance of harvestable trout (>25 cm in total length) as intended but not overall trout abundances. Both rehabilitation techniques also increased maximum channel depth and organic matter retention, but only k-dams increased overall habitat quality. Neither approach significantly affected other ecological variables. The modest ecological response to this habitat improvement likely occurred because the system was not severely degraded beforehand, and thus small, local changes in habitat did not measurably affect most physical and ecological variables measured. However, increases in habitat volume and in organic matter retention may enhance stream biota in the long term.     

Integrative research on environmental and landscape change: PhD students' motivations and challenges

The growing demand for integrative (interdisciplinary or transdisciplinary) approaches in the field of environmental and landscape change has increased the number of PhD students working in this area. Yet, the motivations to join integrative projects and the challenges for PhD students have so far not been investigated. The aims of this paper were to identify the understanding of PhD students with regard to integrative research, their motivations to join integrative projects, their expectations in terms of integration and results, and to reveal the challenges they face in integrative projects. We collected data by a questionnaire survey of 104 PhD students attending five PhD Master Classes held from 2003 to 2006. We used manual content analysis to analyse the free-text answers. The results revealed that students lack a differentiated understanding of integrative approaches. The main motivations to join integrative projects were the dissertation subject, the practical relevance of the project, the intellectual stimulation of working with different disciplines, and the belief that integrative research is more innovative. Expectations in terms of integration were high. Core challenges for integration included intellectual and external challenges such as lack of knowledge of other disciplines, knowledge transfer, reaching depth, supervision, lack of exchange with other students and time demands. To improve the situation for PhD students, we suggest improving knowledge on integrative approaches, balancing practical applicability with theoretical advancement, providing formal introductions to other fields of research, and enhancing institutional support for integrative PhD projects.     

Catalysts and inhibitors for oxidative degradation of monoethanolamine

MEA solutions were subjected to oxidative degradation at both low and high gas rates. Solutions were degraded with 100 mL/min of 98%O₂/2%CO₂ with mass transfer achieved by vortexing. Solutions were analyzed for degradation products by IC and HPLC. In a parallel apparatus 7.5 L/min of 15%O₂/2%CO₂ was sparged through solution, with additional mass transfer achieved by vortexing. A Fourier Transform Infrared (FTIR) analyzer collected continuous gas-phase data on volatile products.Hydroxyethyl-formamide (HEF) and hydroxyethylimidazole (HEI) are the major liquid-phase oxidation products. In the presence of Fe²⁺ and Cu²⁺, HEF, HEI, and MEA losses increase by a factor of 3 compared to Fe²⁺ alone. Cr³⁺ and Ni²⁺, two metals present in stainless steel alloys, resulted in MEA losses that are 55% greater. In terms of oxidative degradation potential (greatest to lowest): Cu²⁺ > Cr³⁺/Ni²⁺ > Fe²⁺ > V⁵⁺.Inhibitor A reduces the formation of known products by 90% when catalyzed by Fe²⁺ and Cu²⁺ and by 99% with Cr³⁺/Ni²⁺. Inhibitor B reduces product rates by 97% and MEA losses by 75%, while a 100:1 ratio of EDTA to Fe²⁺ completely inhibits oxidation.     

Use of mixed technologies to remediate chlorinated DNAPL at a Brownfields site

A former chlorofluorocarbon manufacturing facility in northern New Jersey was purchased for redevelopment as a warehousing/distribution center as part of the New Jersey Department of Environmental Protection's Brownfields redevelopment initiative. Soil and groundwater at the site were impacted with dense nonaqueous‐phase liquids (chlorinated organic compounds) and light nonaqueous‐phase liquids (petroleum hydrocarbons). The initial remedial strategy (excavation and offsite disposal) developed by prior site owners would have been cost‐prohibitive to the new site owners and made redevelopment infeasible. Mixed remedial technologies were employed to reduce the cost of remediation while meeting regulatory contaminant levels that are protective of human health and the environment. The most heavily impacted soils (containing greater than 95 percent of the contaminant mass) were excavated and treated onsite by the addition of calcium oxide and lime kiln dust coupled with physical mixing. Treated soils were reused onsite as part of the redevelopment. Residual soil and groundwater contamination was treated via in situ injections of emulsified oil to enhance anaerobic biodegradation, and emulsified oil/zero‐valent iron to chemically reduce residual contaminants. Engineering (cap) and administrative (deed restriction) controls were used as part of the final remedy. The remedial strategy presented in this article resulted in a cost reduction of 50 percent of the initial remedial cost estimate. © 2008 Wiley Periodicals, Inc.     

Study of the spatial variation of the biodegradation rate of the herbicide bentazone with soil depth using contrasting incubation methods

Vertical and horizontal spatial variability in the biodegradation of the herbicide bentazone was compared in sandy-loam soil from an agricultural field using sieved soil and intact soil cores. An initial experiment compared degradation at five depths between 0 and 80 cm using sieved soil. Degradation was shown to follow the first-order kinetics, and time to 50% degradation (DT(50)), declined progressively with soil depth from 56 d at 0-10 cm to 520 d at 70-80 cm. DT(50) was significantly correlated with organic matter, pH and dehydrogenase activity. In a subsequent experiment, degradation rate was compared after 127 d in sieved soil and intact cores from 0 to 10 and 50 to 60 cm depth from 10 locations across a 160x90 m portion of the field. Method of incubation significantly affected mean dissipation rate, although there were relatively small differences in the amount of pesticide remaining in intact cores and sieved soil, accounting for between 4.6% and 10.6% of that added. Spatial variability in degradation rate was higher in soil from 0 to 10 cm depth relative to that from 50 and 60 cm depth in both sieved soil and intact core assessments. Patterns of spatial variability measured using cores and sieved soil were similar at 50-60 cm, but not at 0-10 cm depth. This could reflect loss of environmental context following processing of sieved soil. In particular, moisture content, which was controlled in sieved soil, was found to be variable in cores, and was significantly correlated with degradation rate in intact topsoil cores from 0 to 10 cm depth.     

Removal of toxic ions (chromate, arsenate, and perchlorate) using reverse osmosis, nanofiltration, and ultrafiltration membranes

Rejection characteristics of chromate, arsenate, and perchlorate were examined for one reverse osmosis (RO, LFC-1), two nanofiltration (NF, ESNA, and MX07), and one ultrafiltration (UF and GM) membranes that are commercially available. A bench-scale cross-flow flat-sheet filtration system was employed to determine the toxic ion rejection and the membrane flux. Both model and natural waters were used to prepare chromate, arsenate, and perchlorate solutions (approximately 100 μg L⁻¹ for each anion) in mixtures in the presence of other salts (KCl, K₂SO₄, and CaCl₂); and at varying pH conditions (4, 6, 8, and 10) and solution conductivities (30, 60, and 115 mS m⁻¹). The rejection of target ions by the membranes increases with increasing solution pH due to the increasingly negative membrane charge with synthetic model waters. Cr(VI), As(V), and rejection follows the order LFC-1 (>90%) > MX07 (25–95%)  ESNA (30–90%) > GM (3–47%) at all pH conditions. In contrast, the rejection of target ions by the membranes decreases with increasing solution conductivity due to the decreasingly negative membrane charge. Cr(VI), As(V), and rejection follows the order CaCl₂ < KCl  K₂SO₄ at constant pH and conductivity conditions for the NF and UF membranes tested. For natural waters the LFC-1 RO membrane with a small pore size (0.34 nm) had a significantly greater rejection for those target anions (>90%) excluding (71–74%) than the ESNA NF membrane (11–56%) with a relatively large pore size (0.44 nm), indicating that size exclusion is at least partially responsible for the rejection. The ratio of solute radius (r_i,s) to effective membrane pore radius (r_p) was employed to compare ion rejection. For all of the ions, the rejection is higher than 70% when the r_i,s/r_p ratio is greater than 0.4 for the LFC-1 membrane, while for di-valent ions (, , and ) the rejection (38–56%) is fairly proportional to the r_i,s/r_p ratio (0.32–0.62) for the ESNA membrane.     

Individual particle characteristics of North African dust under different long-range transport scenarios

After urban sources, mineral dust in Madrid is the second biggest contributor to PM₁₀, making up 40% on average, of total emissions. Approximately, 50% of the days on which the daily limit of 50 μg m^?3 marked by the European Directive, are ascribable to Saharan outbreaks. The present study has focused on individual particle characterization of North African dust over Madrid by SEM/EDX, since no previous works on this type of characterization have been found in the region. More than 30,000 particles from 6 different samples have been measured to characterize 4 African episodes with very different meteorological scenarios, transport processes and source origins. Different samples from the same episode have also been characterized to evaluate homogeneity of dust characteristics over time. Silicates, mainly composed of clay minerals, are the main component, with abundances ranging from 65 to 85% by particle volume. Chemical cluster distribution of silicates has been linked to the major topsoil mineralogical composition in the origin of the episodes. Aspect Ratio (AR) has been used to compare particle morphology between episodes. AR values from samples taken under the same scenarios are statistically equal. For all the samples and size ranges AR values are found to be in the same order: AR_sulphates > AR_silicates > AR_carbonates. Particles not only maintained morphology during the episode, but also chemical composition, since clusters turned out to be very similar in samples taken on the same day and different days. Similarities and differences in particle chemical composition and morphology between the different transport patterns are discussed in detail throughout the paper.     

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.     

Fungicide impacts on microbial communities in soils with contrasting management histories

The impacts of the fungicides azoxystrobin, tebuconazole and chlorothalonil on microbial properties were investigated in soils with identical mineralogical composition, but possessing contrasting microbial populations and organic matter contents arising from different management histories. Degradation of all pesticides was fastest in the high OM/biomass soil, with tebuconazole the most persistent compound, and chlorothalonil the most readily degraded. Pesticide sorption distribution coefficient (K(d)) did not differ significantly between the soils. Chlorothalonil had the highest K(d) (97.3) but K(d) for azoxystrobin and tebuconazole were similar (13.9 and 12.4, respectively). None of the fungicides affected microbial biomass in either soil. However, all fungicides significantly reduced dehydrogenase activity to varying extents in the low OM/biomass soil, but not in the high OM/biomass soil. The mineralization of subsequent applications of herbicides, which represents a narrow niche soil process was generally reduced in both soils by azoxystrobin and chlorothalonil. 16S rRNA-PCR denaturing gradient gel electrophoresis (DGGE) indicated that none of the fungicides affected bacterial community structure. 18S rRNA PCR-DGGE analysis revealed that a small number of eukaryote bands were absent in certain fungicide treatments, with each band being specific to a single fungicide-soil combination. Sequencing indicated these represented protozoa and fungi. Impacts on the specific eukaryote DGGE bands showed no relationship to the extent to which pesticides impacted dehydrogenase or catabolism of herbicides.