Integrated Modular Modeling of Water and Nutrients From Point and Nonpoint Sources in the Patuxent River Watershed1

Abstract: We present a simple modular landscape simulation model that is based on a watershed modeling framework in which different sets of processes occurring in a watershed can be simulated separately with different models. The model consists of three loosely coupled submodels: a rainfall‐runoff model (TOPMODEL) for runoff generation in a subwatershed, a nutrient model for estimation of nutrients from nonpoint sources in a subwatershed, and a stream network model for integration of point and nonpoint sources in the routing process. The model performance was evaluated using monitoring data in the watershed of the Patuxent River, a tributary to the Chesapeake Bay in Maryland, from July 1997 through August 1999. Despite its simplicity, the landscape model predictions of streamflow, and sediment and nutrient loads were as good as or better than those of the Hydrological Simulation Program‐Fortran model, one of the most widely used comprehensive watershed models. The landscape model was applied to predict discharges of water, sediment, silicate, organic carbon, nitrate, ammonium, organic nitrogen, total nitrogen, organic phosphorus, phosphate, and total phosphorus from the Patuxent watershed to its estuary. The predicted annual water discharge to the estuary was very close to the measured annual total in terms of percent errors for both years of the study period (≤2%). The model predictions for loads of nutrients were also good (20‐30%) or very good (<20%) with exceptions of sediment (40%), phosphate (36%), and organic carbon (53%) for Year 1.     

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.     

Effects of short-term pH fluctuations on cadmium, nickel, lead, and zinc availability to ryegrass in a sewage sludge-amended field

In this field experiment, sewage sludge was applied at 0, 5, 10, and 50tha(-1), and the availability of Cd, Ni, Pb, and Zn was assessed both by ryegrass uptake and by DTPA extractions. The aim was to investigate the role of important soil parameters, particularly pH, on heavy metal availability. It was found that metal uptake and extractability increased significantly in the 50tha(-1) treatment. In the 16th week of the experiment there was a significant, although temporary, increase in DTPA-extractable Cd, Ni, and Zn concentrations. Metal concentrations in ryegrass were also significantly elevated in week 20 compared to the subsequent cuttings. These fluctuations in both DTPA and ryegrass uptake occurred only at 50tha(-1) and were probably induced by a sudden pH decrease measured in the same treatment in week 16. This suggests that soils which have received high applications of sewage sludge may be prone to fluctuations in metal availability.     

Heavy metals effects on proteolytic system in sunflower leaves

Plant proteolytic system includes proteases, mainly localized inside the organelles, and the ubiquitin-proteasome pathway in both, the cytoplasm and the nucleus. It was recently demonstrated that under severe Cd stress sunflower (Helianthus annuus L.) proteasome activity is reduced and this results in accumulation of oxidized proteins. In order to test if under other heavy metal stresses sunflower proteolytic system undergoes similar changes, an hydroponic experiment was carried out. Ten days old sunflower plants were transferred to hydroponic culture solutions devoid (control) or containing 100 microM of AlCl(3), CoCl(2), CuCl(2), CrCl(3), HgCl(2), NiCl(2), PbCl(2) or ZnCl(2) and analyzed for protein oxidative damage and proteolytic activities. After 4 days of metal treatment, only Co(2+), Cu(2+), Hg(2+), and Ni(2+) were found to increase carbonyl groups content. Except for Al(3+) and Zn(2+), all metals tested significantly reduced all proteasome activities (chymotrypsin-like, trypsin-like and PGPH) and acid and neutral proteases activities. The effect on basic proteases was more variable. Abundance of 20S protein after metal treatments was similar to that obtained for control samples. Co(2+), Cu(2+), Hg(2+), Ni(2+), Cr(3+), and Pb(2+) induced accumulation of ubiquitin conjugated proteins. It is concluded that heavy metal effects on proteolytic system cannot be generalized; however, impairment of proteasome functionality and decreased proteases activities seem to be a common feature involved in metal toxicity to plants.     

Influence of gas flow-induced shear stress on the operation of the Anammox process in a SBR

The start up and performance of the Anammox process were tested in sequencing batch reactors with two different configurations: a bubble column (SBR-B) and a gas-lift reactor (SBR-G). Different off-gas upflow velocities were tested (3.53-12.3 cm min(-1)) in order to expose the biomass to different shear conditions and to study their effects on both efficiency and physical properties of the Anammox granular biomass. For the SBR-B the minimum gas upflow velocity needed to achieve biomass suspension inside the reactor was 12.3 cm min(-1). Such velocity made impossible the stable operation of the process. The fluidization of biomass for the SBR-G was reached at a gas upflow velocity of 3.52 cm min(-1). This system maintained an efficiency of nitrite removal around 98% at values up to 5.29 cm min(-1) but when the gas upflow velocity was increased from 5.29 to 9.70 cm min(-1) a significant decrease of the specific Anammox activity of the biomass from 0.35 to 0.05 g Ng(-1) VSS d(-1) was measured. The system lost 85% of its nitrogen removal efficiency which was not restored in spite of returning the gas upflow velocity to its initial value.     

Leaching of cyanogenic glucosides and cyanide from white clover green manure

Use of crops for green manure as a substitute for chemical fertilizers and pesticides is an important approach towards more sustainable agricultural practices. Green manure from white clover is rich in nitrogen but white clover also produces the cyanogenic glucosides (CGs) linamarin and lotaustralin; CGs release toxic hydrogen cyanide (HCN) upon hydrolysis which may be utilized for pest control. We demonstrate that applying CGs in the form of a liquid extract of white clover to large columns of intact agricultural soils can result in leaching of toxic cyanide species to a depth of at least 1m. Although degradation of the CGs during leaching proceeded with half lives in the interval 1.5-35 h depending on soil characteristics, a fraction of the applied CGs (0.9-3.2%) was recovered in the leachate as either CGs or toxic cyanide species. Detoxification of the HCN formed was rapid in soil and leachate from both sandy and loamy soil. However, 30% of the leachate samples exceeded the EU threshold value of 50 micrgl(-1) total cyanide for drinking water and 85% exceeded the US threshold of 5 micrgl(-1) for cyanide chronic ecotoxicity in fresh water. This study demonstrates that even easily degradable natural products present in crop plants as defense compounds pose a threat to the quality of groundwater and surface waters. This aspect needs consideration in assessment of the risk associated with use of crops as green manure to replace chemical fertilizers and pesticides as well as in genetic engineering approaches to design crops with improved pest resistance.     

Genotoxicity assessment of acute exposure of chlorpyrifos to freshwater fish Channa punctatus (Bloch) using micronucleus assay and alkaline single-cell gel electrophoresis

Chlorpyrifos (O,O-diethyl O-3,5,6-trichloro-2-pyridylphosphorothioate) is one of the organophosphate pesticides widely used in agricultural practices throughout world and irreversible inhibitor of cholinesterase in all animal species. Limited efforts have been made to study acute genotoxic effects of chlorpyrifos (CPF) in different tissues of fish using genotoxic biomarkers. Therefore, the present investigation was aimed to study the induction of DNA damage by CPF in freshwater teleost fish Channapunctatus using micronucleus assay (MN assay) and alkaline single-cell gel electrophoresis (comet assay). The value of LC(50) - 96 h of CPF was determined as 811.98 microgl(-1) for C. punctatus, in a semi-static system and on the basis of LC(50) value three acute concentrations viz., 203, 406 and 609 microgl(-1) were determined. The fishes were exposed to the different concentrations of CPF for 96 h and samplings were done at regular intervals for assessment of the MN frequencies and DNA damage. In general, significant effects (P<0.01) from both concentrations and time of exposure were observed in exposed fishes. It was found that the micronucleus induction was highest on 96 h at all concentrations in the peripheral blood. Similar trend was observed for the DNA damage measured in terms of the percentage of tail DNA in the lymphocyte and gill cells. This study explored the combined use of micronucleus assay and comet assay for in vivo laboratory studies using fresh water fish for screening the genotoxic potential of xenobiotics.     

Heavy metals in soils: distribution, relationship with soil characteristics and radionuclides and multivariate assessment of contamination sources

The study is dealing with the distribution and the origin of heavy metals (Cd, Cr, Cu, Mn, Ni, Pb and Zn) in soils from a priori non-polluted areas. Positive correlations with organic matter and clay content but not with pH have been observed for most of elements analyzed in this study. Correlations of some metals (Cr, Pb and Zn) and radionuclides (238U and 137Cs) observed for analyzed soils could be explained by their common affinity for clay minerals. Enrichment factor (EF) analysis and cluster analysis (CA) highlighted the lithogenic origin of Cr, Cu, Mn, Ni, Pb and Zn and pointed out the primary input of Cd from anthropogenic sources. It also revealed the need for detailed geochemical surveys in the future in order to decrease the uncertainty of discrimination between lithogenic and anthropogenic origin of metals of interest.     

Polybrominated diphenyl ethers and HBCD in bird eggs of South Africa

In this paper, the first data on brominated flame retardants (BFRs), in particular polybrominated diphenyl ethers (PBDEs) and hexabromocyclododecane (HBCD) in eggs of bird species from South Africa are described (N=43). Concentrations of PBDEs were detected in all the studied species and in all the geographic areas. Highest concentrations of PBDEs were measured in bird eggs from the Vaal River, which is situated downstream of the most industrialized area in South Africa. Sum-PBDE concentrations were highest in eggs of one African sacred ibis (396 ng g(-1) lipid weight (lw)), possibly due to foraging on dumping sites. Lowest mean level of sum-PBDEs (2.3 ng g(-1) lw) was measured in cattle egrets (N=11) from Barberspan Sanctuary, a Ramsar site. The PBDE congener pattern showed large differences, reflecting different trophic levels, migratory behavior, distance to the source, and, exposure to different PBDE mixtures, among others. HBCD was detected only in four species, and highest levels were measured in one egg of African sacred ibis (71 ng g(-1) lw). In most species, levels of PBDEs were one to several orders of magnitude lower than levels of DDTs and PCBs. PBDEs correlated strongly with DDTs, PCBs and some other organochlorines (OCs), indicating the same source. The widespread occurrence of PBDEs in the South African avian species showed a strong need for further investigations of PBDEs in the Southern African environment.     

Antioxidant enzyme activities as affected by trivalent and hexavalent chromium species in Fontinalis antipyretica Hedw

The detoxification mechanisms of the aquatic moss, Fontinalis antipyretica Hedw., exposed to Cr was analyzed. In addition, the influence of Cr salts (as Cr nitrate, chloride and potassium bichromate) on these mechanisms has also been studied. The activity of antioxidant enzymes superoxide dismutase (SOD, EC 1.15.1.1.), catalase (EC 1.11.1.6.), ascorbate peroxidase (APX, EC 1.11.1.11.), guaiacol peroxidase (GPX, EC 1.11.1.7.) and glutathione reductase (GR, EC 1.6.4.2.) increased in plants treated with Cr concentrations ranging from 6.25x10(-5) to 6.25mM when given as Cr(NO(3))(3). Antioxidant enzymes responded to the other two salts CrCl(3) and K(2)Cr(2)O(7) only with Cr concentrations higher than 6.25x10(-2)mM. Glutathione level and GSSG/GSH ratio also responded to Cr exposure but no dose-effect relationship could be observed. Moreover, two unknown thiol compounds were observed in mosses exposed to the highest Cr concentrations. Effects on chlorophyll contents and chlorophyll a/b ratios were also shown even at low Cr concentrations. Our results indicated that environmentally realistic concentrations of Cr could lead to impairment of the cellular activity towards F. antipyretica and that Cr(III), when present as a nitrate salt, was as harmful as Cr(VI).