Atrazine leaching through surface and subsurface of a tropical Oxisol

The fate of (14)C atrazine was investigated using microcosms and an undisturbed Red-Yellow Latossol (Oxisol) under simulated rainfall conditions of 200 mm water month(-1). Experiments were carried out using microcosm cores, the first with an uncovered surface soil; the second set with uncovered subsurface soil; the third with subsurface soil covered with 3 cm of cow manure and the last with subsurface soil covered with 5 cm of grass straw. Average values for the amount of atrazine leached after 60 days were as follows: surface soil 1.6%; subsurface 47.3%; subsurface plus manure 17.3% and subsurface plus straw 24.8%. In the surface soil, 53% of the (14)C atrazine remained within the upper 1 cm, while in the subsurface microcosms the atrazine was more evenly distributed. The authors report that surface soil was retained atrazine and its metabolites for 60 days. The addition of a straw or manure covering to exposed subsoil helped to retard atrazine leaching.     

Influence of synthetic surfactants on the uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca

Uptake of Pd, Cd and Pb by the marine macroalga, Ulva lactuca, has been studied in the presence of an anionic (sodium dodecyl sulphate, SDS), cationic (hexadecyltrimethylammonium bromide; HDTMA) and non-ionic (Triton X-100; TX) surfactant. Compared with the surfactant-free system, metal sorption was reduced in the presence of SDS or TX. Neither surfactant, however, had any measurable impact on cell membrane permeability, determined by leakage of dissolved free amino acids (DFAA), or on metal internalisation. We attribute these observations to the stabilisation of aqueous Cd and Pb by SDS and the shielding of otherwise amenable sorption sites by TX. Presence of HDTMA resulted in a reduction in the extent of both sorption and internalisation of all metals and a significant increase in the leakage of DFAA. Thus, by enhancing membrane permeability, HDTMA exerts the greatest influence on metal behaviour in the presence of U. lactuca.     

Influence of a soil enzyme on iron-cyanide complex speciation and mineral adsorption

Cyanide is commonly found as ferrocyanide [Fe(II)(CN)(6)](-4) and in the more mobile form, ferricyanide [Fe(III)(CN)(6)](-3) in contaminated soils and sediments. Although soil minerals may influence ferrocyanide speciation, and thus mobility, the possible influence of soil enzymes has not been examined. In a series of experiments conducted under a range of soil-like conditions, laccase, a phenoloxidase enzyme derived from the fungi Trametes versicolor, was found to exert a large influence on iron-cyanide speciation and mobility. In the presence of laccase, up to 93% of ferrocyanide (36-362ppm) was oxidized to ferricyanide within 4h. No significant effect of pH (3.6 and 6.2) or initial ferrocyanide concentration on the extent or rate of oxidation was found and ferrocyanide oxidation did not occur in the absence of laccase. Relative to iron-cyanide-mineral systems without laccase, ferrocyanide adsorption to aluminum hydroxide and montmorillonite decreased in the presence of laccase and was similar to or somewhat greater than that of ferricyanide without laccase. Laccase-catalyzed conversion of ferrocyanide to ferricyanide was extensive though up to 33% of the enzyme was mineral-bound. These results demonstrate that soil enzymes can play a major role in ferrocyanide speciation and mobility. Biotic soil components must be considered as highly effective oxidation catalysts that may alter the mobility of metals and metal complexes in soil. Immobilized enzymes should also be considered for use in soil metal remediation efforts.     

Remediation of PAH contaminated soils: application of a solid-liquid two-phase partitioning bioreactor

The feasibility of a two-step treatment process has been assessed at laboratory scale for the remediation of soil contaminated with a model mixture of polycyclic aromatic hydrocarbons (PAHs) (phenanthrene, pyrene, and fluoranthene). The initial step of the process involved contacting contaminated soil with thermoplastic, polymeric pellets (polyurethane). The ability of three different mobilizing agents (water, surfactant (Biosolve) and isopropyl alcohol) to enhance recovery of PAHs from soil was investigated and the results were compared to the recovery of PAHs from dry soil. The presence of isopropyl alcohol had the greatest impact on PAH recovery with approximately 80% of the original mass of PAHs in the soil being absorbed by the polymer pellets in 48 h. The second stage of the suggested treatment involved regeneration of the PAH loaded polymers via PAH biodegradation, which was carried out in a solid-liquid two-phase partitioning bioreactor. In addition to the PAH containing polymer pellets, the bioreactor contained a microbial consortium that was pre-selected for its ability to degrade the model PAHs and after a 14 d period approximately 78%, 62% and 36% of phenanthrene, pyrene, and fluoranthene, respectively, had been desorbed from the polymer and degraded. The rate of phenanthrene degradation was shown to be limited by mass transfer of phenanthrene from the polymer pellets. In case of pyrene and fluoranthene a combination of mass transfer and biodegradation rate might have been limiting.     

Laboratory investigation of flux reduction from dense non-aqueous phase liquid (DNAPL) partial source zone remediation by enhanced dissolution

This study investigated the benefits of partial removal of dense nonaqueous phase liquid (DNAPL) source zones using enhanced dissolution in eight laboratory scale experiments. The benefits were assessed by characterizing the relationship between reductions in DNAPL mass and the corresponding reduction in contaminant mass flux. Four flushing agents were evaluated in eight controlled laboratory experiments to examine the effects of displacement fluid property contrasts and associated override and underride on contaminant flux reduction (R(j)) vs. mass reduction (R(m)) relationships (R(j)(R(m))): 1) 50% ethanol/50% water (less dense than water), 2) 40% ethyl-lactate/60% water (more dense than water), 3) 18% ethanol/26% ethyl-lactate/56% water (neutrally buoyant), and 4) 2% Tween-80 surfactant (also neutrally buoyant). For each DNAPL architecture evaluated, replicate experiments were conducted where source zone dissolution was conducted with a single flushing event to remove most of the DNAPL from the system, and with multiple shorter-duration floods to determine the path of the R(j)(R(m)) relationship. All of the single-flushing experiments exhibited similar R(j)(R(m)) relationships indicating that override and underride effects associated with cosolvents did not significantly affect the remediation performance of the agents. The R(j)(R(m)) relationship of the multiple injection experiments for the cosolvents with a density contrast with water tended to be less desirable in the sense that there was less R(j) for a given R(m). UTCHEM simulations supported the observations from the laboratory experiments and demonstrated the capability of this model to predict R(j)(R(m)) relationships for non-uniformly distributed NAPL sources.     

Field comparison of manual and semi-automatic methods for the measurement of total gaseous mercury in ambient air and assessment of equivalence

The manual and semi-automatic methods for the measurement of total gaseous mercury in ambient air have been compared in a field trial for the first time. The comparison results have shown that whilst the expected random scatter is present, there was no significant systematic bias between the two methods, whose operational differences have also been outlined and analysed in this work. Furthermore it has been observed that because variation in instrument sensitivity is largely random in nature there is little effect on the results of the comparison if the period between instrument calibrations is altered. When the manual and semi-automatic methods are compared according to guidelines produced by the European Commission the results presented here, taken together with other supporting evidence, strongly suggest that the two methods are equivalent.     

Assessment of prenatal mercury exposure in a predominately Caribbean immigrant community in Brooklyn, NY

Prenatal mercury exposure and its fetotoxic effects may be of particular concern in urban immigrant communities as a result of possible contributing cultural factors. The most common source of exposure in these communities is ingestion of fish and shellfish contaminated with methylmercury. Other sources of exposure may occur in ritualistic practices associated with Hispanic and Caribbean-based religions. This study 1) assessed total mercury levels in both random urine specimens from pregnant women, and in cord blood; and 2) examined environmental sources of exposure from a convenience sample in a predominantly Caribbean immigrant population in Brooklyn, New York. A questionnaire designed in collaboration with health professionals from the Caribbean community assessed the frequency of fish consumption, ritualistic practices, occupational exposures, and use of dental amalgams and mercury-containing skin and household products. The geometric mean for total mercury in cord blood was 2.14 μg L(-1) (95%CI: 1.76-2.60) (n = 78), and 0.45 μg L(-1) (95%CI: 0.37-0.55) (n = 183) in maternal urine corrected for creatinine (μg g(-1)). Sixteen percent of cord blood mercury levels exceeded the estimated equivalent of U.S. Environmental Protection Agency's Reference Dose (5.8 μg L(-1) blood). Predictors of cord blood mercury included maternal fish consumption and foreign birth of the mother. Predictors of urine mercury included foreign birth of the mother, number of dental amalgams, and special product use. There were no reports of mercury use in ritualistic practices or in cosmetics; however some women reported use of religious medals and charms. This study characterized risk factors for mercury exposure in a sample of urban, predominantly Caribbean-born blacks. Findings may help target interventions in this population, which might include appropriate fish selection and consumption frequency during pregnancy, and safe handling of mercury-containing products in the home.     

Preparation and measurement methods for studying nanoparticle aggregate surface chemistry

Despite best efforts at controlling nanoparticle (NP) surface chemistries, the environment surrounding nanomaterials is always changing and can impart a permanent chemical memory. We present a set of preparation and measurement methods to be used as the foundation for studying the surface chemical memory of engineered NP aggregates. We attempt to bridge the gap between controlled lab studies and real-world NP samples, specifically TiO(2), by using well-characterized and consistently synthesized NPs, controllably producing NP aggregates with precision drop-on-demand inkjet printing for subsequent chemical measurements, monitoring the physical morphology of the NP aggregate depositions with scanning electron microscopy (SEM), acquiring "surface-to-bulk" mass spectra of the NP aggregate surfaces with time-of-flight secondary ion mass spectrometry (ToF-SIMS), and developing a data analysis scheme to interpret chemical signatures more accurately from thousands of data files. We present differences in mass spectral peak ratios for bare TiO(2) NPs compared to NPs mixed separately with natural organic matter (NOM) or pond water. The results suggest that subtle changes in the local environment can alter the surface chemistry of TiO(2) NPs, as monitored by Ti(+)/TiO(+) and Ti(+)/C(3)H(5)(+) peak ratios. The subtle changes in the absolute surface chemistry of NP aggregates vs. that of the subsurface are explored. It is envisioned that the methods developed herein can be adapted for monitoring the surface chemistries of a variety of engineered NPs obtained from diverse natural environments.     

A primer for nonresponse in the US forest inventory and analysis program

Nonresponse caused by denied access and hazardous conditions are a concern for the USDA Forest Service, Forest Inventory and Analysis (FIA) program, whose mission is to quantify status and trends in forest resources across the USA. Any appreciable amount of nonresponse can cause bias in FIA’s estimates of population parameters. This paper will quantify the magnitude of nonresponse and describe the mechanisms that result in nonresponse, describe and qualitatively evaluate FIA’s assumptions regarding nonresponse, provide a recommendation concerning plot replacement strategies, and identify appropriate strategies to pursue that minimize bias. The nonresponse rates ranged from 0% to 21% and differed by land owner group; with denied access to private land the leading cause of nonresponse. Current FIA estimators assume that nonresponse occurs at random. Although in most cases this assumption appears tenable, a qualitative assessment indicates a few situations where the assumption is not tenable. In the short-term, we recommend that FIA use stratification schemes that make the missing at random assumption tenable. We recommend the examination of alternative estimation techniques that use appropriate weighting and auxiliary information to mitigate the effects of nonresponse. We recommend the replacement of nonresponse sample locations not be used.