Atrazine and alachlor transport in claypan soils as influenced by differential antecedent soil water content

Increased attention to ground water contamination has encouraged an interest in mechanisms of solute transport through soils. Few studies have investigated the effect of the initial soil water content on the transport and degradation of herbicides for claypan soils. We investigated the effect of claypan soils at initial field capacity vs. permanent wilting level on atrazine and alachlor transport. The soil studied was Mexico silt loam (fine, smectitic, mesic Aeric Vertic Epiaqualf) with a subsoil clay content, primarily montmorillonite, of >40%. Strontium bromide, atrazine, and alachlor were applied to plots; half were at field capacity (Wet treatment), and half were near the permanent wilting point (Dry treatment). Soil cores were removed at selected depths and times, and cores were analyzed for bromide and herbicide concentrations. Bromide, atrazine, and alachlor were detected at the 0.90-m depth in dry plots within 15 d after experiment initiation. Bromide was detected 0.15 m deeper (P < 0.05) in the Dry compared with the Wet treatment at 1, 7, and 60 d after application and >0.30 m deeper (P < 0.01) in the Dry treatment at 15 and 30 d after application; similar treatment results were found for atrazine and alachlor, although on fewer dates with significant differences. The mobility order of the applied chemicals was bromide > atrazine > alachlor. The atrazine apparent half-life was significantly longer in the Dry plots compared with the Wet plots. The retardation factor determined from the relative velocity of each herbicide to that of bromide was higher for alachlor than for atrazine. This study identifies the impact that shrinkage cracks have for different moisture conditions on preferential transport of herbicides in claypan soils.     

Sorption of the veterinary antimicrobials sulfadimethoxine and ormetoprim in soil

Currently, limited research on the fate of antimicrobials in the environment exists, once they are discharged in human and animal wastes. Sorption of two antimicrobials, sulfadimethoxine (SDM) and ormetoprim (OMP), was investigated in two soils and sand using a series of batch experiments. Because OMP and SDM are often administered in combination, their sorption was also investigated in combination as co-solutes. The rate of SDM and OMP sorption was rapid over the first few hours of the experiments, which then slowed considerably after 16 to 68 h. OMP sorption was enhanced at high concentrations when in combination with SDM, with linear sorption coefficients ranging from 1.3 to 58.3 L.kg(-1) in the single solute experiments and 4.96 to 89.7 L.kg(-1) in the co-solute experiments. Sorption of OMP as a single solute seems to provide a better fit with the Freundlich equation, which became more linear (n approached 1) when SDM was present. Overall, SDM sorbed less than OMP in the two soils and sand. SDM linear sorption coefficients ranged from 0.4 to 25.8 L.kg(-1) as a single solute and 2.5 to 22.1 L.kg(-1) as a co-solute. Sorption of SDM becomes more nonlinear (n < 1) when SDM is present in combination with OMP. Overall, sorption of both antimicrobials increased in the selected soils and sand as the organic matter, clay content, and cation exchange capacity increased. These experiments indicate relatively low sorption of SDM and OMP in natural soils, making them a potential threat to surface and ground water.     

Whole-stream response to nitrate loading in three streams draining agricultural landscapes

Physical, chemical, hydrologic, and biologic factors affecting nitrate (NO3(-)) removal were evaluated in three agricultural streams draining orchard/dairy and row crop settings. Using 3-d "snapshots" during biotically active periods, we estimated reach-level NO3(-) sources, NO3(-) mass balance, in-stream processing (nitrification, denitrification, and NO3(-) uptake), and NO3(-) retention potential associated with surface water transport and ground water discharge. Ground water contributed 5 to 11% to stream discharge along the study reaches and 8 to 42% of gross NO3(-) input. Streambed processes potentially reduced 45 to 75% of ground water NO3(-) before discharge to surface water. In all streams, transient storage was of little importance for surface water NO3(-) retention. Estimated nitrification (1.6-4.4 mg N m(-2) h(-1)) and unamended denitrification rates (2.0-16.3 mg N m(-2) h(-1)) in sediment slurries were high relative to pristine streams. Denitrification of NO3(-) was largely independent of nitrification because both stream and ground water were sources of NO3(-). Unamended denitrification rates extrapolated to the reach-scale accounted for <5% of NO3(-) exported from the reaches minimally reducing downstream loads. Nitrate retention as a percentage of gross NO3(-) inputs was >30% in an organic-poor, autotrophic stream with the lowest denitrification potentials and highest benthic chlorophyll a, photosynthesis/respiration ratio, pH, dissolved oxygen, and diurnal NO3(-) variation. Biotic processing potentially removed 75% of ground water NO3(-) at this site, suggesting an important role for photosynthetic assimilation of ground water NO3(-) relative to subsurface denitrification as water passed directly through benthic diatom beds.     

Carbon monoxide from composting due to thermal oxidation of biomass

Emissions of carbon monoxide (CO) were observed from decomposing organic wastes and litter under laboratory, pilot composting plant, and natural conditions. Field studies included air from inside a compost heap of about 200 m3, emissions from composting of livestock wastes at a biologically operating farm, and leaf litter pile air samples. The concentration of CO was up to 120 micromol mol(-1) in the compost piles of green waste, and up to 10 micromol mol(-1) in flux chambers above livestock waste windrow composts. The mean CO flux rates were approximately 20 mg CO m(-2) h(-1) for compost heaps of green waste, and varied from 30 to 100 mg CO m(-2) h(-1) for fresh dung windrows. Laboratory studies using a temperature and ventilation-controlled substrate container were performed to elucidate the origin of CO, and included hay samples of fixed moisture content at temperatures between 5 and 65 degrees C, including nonsterilized as well as sterilized samples. The concentration of CO was up to 160 micromol mol(-1) in these experiments, and Arrhenius-type plot analyses resulted in activation energies of 65 kJ mol(-1) for thermochemically produced CO from the nonsterilized compost substrate. Sterilized samples showed dramatically reduced CO2 but virtually unchanged CO emissions, albeit at a slightly lower activation energy, likely a result of the high-temperature sterilization. Though globally and regionally these CO emissions are only a minor source, thermochemically produced CO emissions might affect local air quality in and near composting facilities.     

Influence of prairie restoration on CT-measured soil pore characteristics

Restored prairies are expected to improve soil physical properties, yet little is known about the extent of change to soil properties and how rapidly these changes take place. The objective of this study was to compare effects of prairie restoration on computed tomography (CT)-measured pore parameters. Undisturbed soil cores (76 mm diam. by 76 mm long) from native prairie (NP), restored prairie (RP), conservation reserve program (CRP), and no-till corn (Zea mays L.)-soybean (Glycine max (L.) Merr.; CS) sites were collected with six replicates from the 0- to 40-cm depth in 10-cm increments. Five CT images were acquired from each soil core using a medical CT scanner with 0.2 by 0.2 mm pixel resolution with 0.5 mm slice thickness, and then images were analyzed. Soil bulk density and hydraulic conductivity (K(sat)) were also measured. Soils under NP, RP, CRP, and CS areas had 83, 43, 48, and 26 pores on a 2500 mm(2) area, respectively, for the 0- to 40-cm depth. The number of pores, number of macropores (>1000 microm diam.), macroporosity, mesoporosity (200-1000 microm diam.), and fractal dimension were significantly higher and pore circularity was lower for NP, RP, and CRP than the CS treatment. The CT-measured mesoporosity and macroporosity of the CS treatment were 20 and 18% of the values for the NP site. CT-measured number of pores and macropores explained 43 and 40% of the variation for K(sat). The study showed that prairie restoration improves CT-measured soil pore parameters and decreases bulk density which are related to soil water infiltration.     

Analyzing the Impacts of Dams on Riparian Ecosystems: A Review of Research Strategies and Their Relevance to the Snake River Through Hells Canyon

River damming provides a dominant human impact on river environments worldwide, and while local impacts of reservoir flooding are immediate, subsequent ecological impacts downstream can be extensive. In this article, we assess seven research strategies for analyzing the impacts of dams and river flow regulation on riparian ecosystems. These include spatial comparisons of (1) upstream versus downstream reaches, (2) progressive downstream patterns, or (3) the dammed river versus an adjacent free-flowing or differently regulated river(s). Temporal comparisons consider (4) pre- versus post-dam, or (5) sequential post-dam conditions. However, spatial comparisons are complicated by the fact that dams are not randomly located, and temporal comparisons are commonly limited by sparse historic information. As a result, comparative approaches are often correlative and vulnerable to confounding factors. To complement these analyses, (6) flow or sediment modifications can be implemented to test causal associations. Finally, (7) process-based modeling represents a predictive approach incorporating hydrogeomorphic processes and their biological consequences. In a case study of Hells Canyon, the upstream versus downstream comparison is confounded by a dramatic geomorphic transition. Comparison of the multiple reaches below the dams should be useful, and the comparison of Snake River with the adjacent free-flowing Salmon River may provide the strongest spatial comparison. A pre- versus post-dam comparison would provide the most direct study approach, but pre-dam information is limited to historic reports and archival photographs. We conclude that multiple study approaches are essential to provide confident interpretations of ecological impacts downstream from dams, and propose a comprehensive study for Hells Canyon that integrates multiple research strategies.     

Characterizing Storm Hydrograph Rise and Fall Dynamics With Stream Stage Data1

Abstract: Storm‐flow transients (i.e., hydrograph rise and fall dynamics) may represent an important aspect of understanding streamflow dynamics. However, little is known about how temporal resolution of transient data and climate variability may color these potential indicators of hydrologic pattern or condition. Warm‐season stream stage and rainfall were monitored continuously (5 min) during the 2002 water year in eight tributaries of the Little Miami River (Ohio), which drain 17‐58 km² catchments. Rise rates generated using 5‐min data were different than those generated with mean daily data [calculated with the Indicators of Hydrologic Alteration (IHA) software], though fall rates were similar for fine and coarse temporal data. This result suggests that data with low temporal resolution may not be adequate to fully represent the dynamics of storm rise rates. Conversely, fall rates based on daily stage data (via IHA) were similar to those based on the 5‐min data, and so daily mean data may be appropriate for characterizing fall rates. We next analyzed the possible correlations between rainfall variability and storm‐flow stage dynamics. We derived rise and recession rates from storm stage hydrographs by assuming exponential rise and decay of a runoff peak. We found that raw rise rates (R_raw) were correlated with both the maximum rainfall rate and the time to the centroid of a rain event. We subsequently removed the trend based on these rainfall characteristics, which yielded new representations of rise rates abbreviated as R_rate and R_tcent, respectively, and that had lower variability than the uncorrected (raw) data. Fall rates were found to be independent of rainfall characteristics. Due to the predominant influence of stream hydrology upon aquatic biota and nutrient fluxes, our work suggests that these stage data analysis protocols can refine or otherwise reduce variability in these indices by accounting for relevant factors such as rainfall forcing. These protocols for derivation of transient indices should be tested for their potential to improve correlations between stream hydrology and temporally aligned biotic data and dissolved nutrient fluxes in streams.     

Comparative study of chromium biosorption by red, green and brown seaweed biomass

Dried biomass of the macroalgae Fucus vesiculosus and Fucus spiralis (brown), Ulva spp. (comprising Ulva linza, Ulva compressa and Ulva intestinalis) and Ulva lactuca (green), Palmaria palmata and Polysiphonia lanosa (red) were studied in terms of their chromium biosorption performance. Metal sorption was highly pH dependent with maximum Cr(III) and Cr(VI) sorption occurring at pH 4.5 and pH 2, respectively. Extended equilibrium times were required for Cr(VI) binding over Cr(III) binding (180 and 120min, respectively) thus indicating possible disparities in binding mechanism between chromium oxidation states. The red seaweed P. palmata revealed the highest removal efficiency for both Cr(III) and Cr(VI) at low initial concentrations. However, at high initial metal concentrations F. vesiculosus had the greatest removal efficiency for Cr(III) and performed almost identically to P. lanosa in terms of Cr(VI) removal. The Langmuir Isotherm mathematically described chromium binding to the seaweeds where F. vesiculosus had the largest q(max) for Cr(III) sorption (1.21mmol g(-1)) and P. lanosa had the largest Cr(VI) uptake (0.88mmol g(-1)). P. palmata had the highest affinity for both Cr(III) and Cr(VI) binding with b values of 4.94mM(-1) and 8.64mM(-1), respectively. Fourier transform infrared analysis revealed interactions of amino, carboxyl, sulphonate and hydroxyl groups in chromium binding to Ulva spp. The remaining seaweeds showed involvement of these groups to varying degrees as well as ether group participation in the brown seaweeds and for Cr(VI) binding to the red seaweeds.     

Polychlorinated biphenyls (PCBs) and hydroxy-PCBs in adipose tissue of women in Southeast Spain

Polychlorinated biphenyls (PCBs) and hydroxylated PCBs (OH-PCBs) were investigated in human adipose tissue samples collected from 20 women undergoing surgery. Mean sum of PCB and sum of OH-PCB levels were 737ng/g of lipid and 8pg/g of lipid, respectively. Among PCBs, congeners 180, 153, 138 and 170 were the most frequent and abundant, and together constituted 72% of the total amount of PCBs in adipose tissue. The PCB congener pattern and the frequencies and concentrations of non-dioxin-like and non-hydroxylated congeners observed in adipose tissue were similar in distribution and order of magnitude to the profile previously published in Spain but lower than that found in other European countries. Among OH-PCB congeners studied, 4-OH-PCB 107/118 was found at the highest concentrations followed by 3'-OH-PCB 180 and 3-OH-PCB 138. To date, no information on levels of PCB metabolites in the Spanish population is available for comparison. These three predominant OH-PCBs contributed 97% of all OH-PCBs. Twelve dioxin-like PCBs contributed around 8% of the total PCB exposure, and all were present in all study subjects. Further research is required to determine trends in human exposure to PCBs and OH-PCBs and how existing banning measures affect exposure.     

Photochemical degradation of methylparathion in the presence of humic acid

Photochemical degradation of methylparathion (O,O,-dimethyl O-4 nitrophenylphosphorothioate) in the presence of humic acid between pH 2 and 7 was monitored by differential pulse polarography. Humic acid was not electro-active under the experimental conditions used in this study. Only the pesticide and its main degradation product at pH 2 exhibited polarographic signals. Photolysis of methylparathion in acid media was sensitized by humic acid since the pesticide did not degrade in the absence of this compound. Methylparathion degradation in the presence of humic acid was observed at each of the studied pHs. The reaction was first-order with rate constant values ranging from 2 x 10(-3) to 6.3 x 10(-3) min(-1).