Occurrence and fate of pesticides in four contrasting agricultural settings in the United States

Occurrence and fate of 45 pesticides and 40 pesticide degradates were investigated in four contrasting agricultural settings--in Maryland, Nebraska, California, and Washington. Primary crops included corn at all sites, soybeans in Maryland, orchards in California and Washington, and vineyards in Washington. Pesticides and pesticide degradates detected in water samples from all four areas were predominantly from two classes of herbicides--triazines and chloroacetanilides; insecticides and fungicides were not present in the shallow ground water. In most samples, pesticide degradates greatly exceeded the concentrations of parent pesticide. In samples from Nebraska, the parent pesticide atrazine [6-chloro-N-ethyl-N'-(1-methylethyl)-1,3,5-triazine-2,4-diamine] was about the same concentration as the degradate, but in samples from Maryland and California atrazine concentrations were substantially smaller than its degradate. Simazine [6-chloro-N,N'-diethyl-1,3,5-triazine-2,4-diamine], the second most detected triazine, was detected in ground water from Maryland, California, and Washington. Metolachlor [2-chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl)acetamide] rarely was detected without its degradates, and when they were detected in the same sample metolachlor always had smaller concentrations. The Root-Zone Water-Quality Model was used to examine the occurrence and fate of metolachlor at the Maryland site. Simulations accurately predicted which metolachlor degradate would be predominant in the unsaturated zone. In analyses of relations among redox indicators and pesticide variance, apparent age, concentrations of dissolved oxygen, and excess nitrogen gas (from denitrification) were important indicators of the presence and concentration of pesticides in these ground water systems.     

Adsorption-desorption characteristics of mercury in paddy soils of China

Mercury (Hg) has received considerable attention because of its association with various human health problems. Adsorption-desorption behavior of Hg at contaminated levels in two paddy soils was investigated. The two representative soils for rice production in China, locally referred to as a yellowish red soil (YRS) and silty loam soil (SLS) and classified as Gleyi-Stagnic Anthrosols in FAO/UNESCO nomenclature, were respectively collected from Jiaxin County and Xiasha District of Hangzhou City, Zhejiang Province. The YRS adsorbed more Hg(2+) than the SLS. The characteristics of Hg adsorption could be described by the simple Langmuir adsorption equation (r2 = 0.999 and 0.999, P < 0.01, respectively, for the SLS and YRS). The maximum adsorption values (Xm) that were obtained from the simple Langmuir model were 111 and 213 mg Hg(2+) kg(-1) soil, respectively, for the SLS and YRS. Adsorption of Hg(2+) decreased soil pH by 0.75 unit for the SLS soil and 0.91 unit for the YRS soil at the highest loading. The distribution coefficient (kd) of Hg in the soil decreased exponentially with increasing Hg(2+) loading. After five successive desorptions with 0.01 mol L(-1) KCl solution (pH 5.4), 0 to 24.4% of the total adsorbed Hg(2+) in the SLS soil was desorbed and the corresponding value of the YRS soil was 0 to 14.4%, indicating that the SLS soil had a lower affinity for Hg(2+) than the YRS soil at the same Hg(2+) loading. Different mechanisms are likely involved in Hg(2+) adsorption-desorption at different levels of Hg(2+) loading and between the two soils.     

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.     

Blowing Smoke in Yellowstone: Air Quality Impacts of Oversnow Motorized Recreation in the Park

Snowmobile use in Yellowstone National Park has been shown to impact air quality, with implications for the safety and welfare of Park staff and other Park resource values. Localized impacts have been documented at several high-use sites in the Park, but the broader spatial variability of snowmobile emissions and air quality was not understood. Measurements of 87 volatile organic compounds (VOCs) were made for ambient air sampled across the Park and West Yellowstone, Montana, during 2 days of the 2002–2003 winter use season, 1 year before the implementation of a new snowmobile policy. The data were compared with similar data from pristine West Coast sites at similar latitudes. Backward trajectories of local air masses, alkyl nitrate-parent alkane ratios, and atmospheric soundings were used to identify the VOC sources and assess their impact. Different oversnow vehicle types used in the Park were sampled to determine their relative influence on air mass pollutant composition. VOCs were of local origin and demonstrated strong spatiotemporal variability that is primarily influenced by levels of snowmobile traffic on given road segments at different times of day. High levels of snowmobile traffic in and around West Yellowstone produced consistently high levels of benzene, toluene, and carbon monoxide.     

Removal and degradation of aromatic compounds from a highly polluted site by coupling soil washing with photocatalysis

The possible application of two environmental remediation technologies - soil washing and photocatalysis - to remove and decompose various aromatic pollutants present in excavated soils of a contaminated industrial site has been investigated. Aqueous solutions containing the non-ionic surfactant Brij 35 were used to extract the contaminants from the soil samples. The photocatalytic treatment of the obtained washing wastes, performed in the presence of TiO(2) suspensions irradiated with simulated sunlight, showed a slow abatement of the toxic compounds due to the relevant concentrations of organics in the waste. A neat improvement of the process performances, obtained by operating in the presence of added potassium peroxydisulfate, suggests a feasible treatment route.     

Ozonation of oil sands process water removes naphthenic acids and toxicity

Naphthenic acids are naturally-occurring, aliphatic or alicyclic carboxylic acids found in petroleum. Water used to extract bitumen from the Athabasca oil sands becomes toxic to various organisms due to the presence of naphthenic acids released from the bitumen. Natural biodegradation was expected to be the most cost-effective method for reducing the toxicity of the oil sands process water (OSPW). However, naphthenic acids are poorly biodegraded in the holding ponds located on properties leased by the oil sands companies. In the present study, chemical oxidation using ozone was investigated as an option for mitigation of this toxicity. Ozonation of sediment-free OSPW was conducted using proprietary technology manufactured by Seair Diffusion Systems Inc. Ozonation for 50min generated a non-toxic effluent (based on the Microtox bioassay) and decreased the naphthenic acids concentration by approximately 70%. After 130min of ozonation, the residual naphthenic acids concentration was 2mgl(-1): <5% of the initial concentration in the filtered OSPW. Total organic carbon did not change with 130min of ozonation, whereas chemical oxygen demand decreased by approximately 50% and 5-d biochemical oxygen demand increased from an initial value of 2mgl(-1) to a final value of 15mgl(-1). GC-MS analysis showed that ozonation resulted in an overall decrease in the proportion of high molecular weight naphthenic acids (n> or = 22).     

An enzyme-linked immunosorbent assay for the determination of dioxins in contaminated sediment and soil samples

A 96-microwell enzyme-linked immunosorbent assay (ELISA) method was evaluated to determine PCDDs/PCDFs in sediment and soil samples from an EPA Superfund site. Samples were prepared and analyzed by both the ELISA and a gas chromatography/high resolution mass spectrometry (GC/HRMS) method. Comparable method precision, accuracy, and detection level (8 ng kg(-1)) were achieved by the ELISA method with respect to GC/HRMS. However, the extraction and cleanup method developed for the ELISA requires refinement for the soil type that yielded a waxy residue after sample processing. Four types of statistical analyses (Pearson correlation coefficient, paired t-test, nonparametric tests, and McNemar's test of association) were performed to determine whether the two methods produced statistically different results. The log-transformed ELISA-derived 2,3,7,8-tetrachlorodibenzo-p-dioxin values and log-transformed GC/HRMS-derived TEQ values were significantly correlated (r=0.79) at the 0.05 level. The median difference in values between ELISA and GC/HRMS was not significant at the 0.05 level. Low false negative and false positive rates (<10%) were observed for the ELISA when compared to the GC/HRMS at 1,000 ng TEQ kg(-1). The findings suggest that immunochemical technology could be a complementary monitoring tool for determining concentrations at the 1,000 ng TEQ kg(-1) action level for contaminated sediment and soil. The ELISA could also be used in an analytical triage approach to screen and rank samples prior to instrumental analysis.     

Effects of concentrated drinking water injection on glutathione and glutathione-dependent enzymes in liver of Cyprinus carpio L

Two drinking water production plants located in North Italy, collecting water from the River Po (Plants 1 and 2) were chosen for this study. Water samples were collected before and after the disinfection process and at two points along the piping system. Water samples were concentrated by the solid-phase extraction system and injected intraperitoneally into specimens of Cyprinus carpio. The concentration of water samples was 3 l/equiv. In order to assess the effects of the water samples on carp liver, total glutathione and glutathione-dependent enzymes, such as glutathione S-transferase, glutathione peroxidase, glutathione reductase and glyoxalase I, were measured following this treatment for 6 days at two experimental times (3 and 6 days). Both water plant-treated carp showed a general increase of the enzymatic activities of glutathione S-transferase, and glutathione reductase which might be employed as potential biomarkers of oxidative stress induced by disinfected river water. Plant 1-treated carp showed higher glyoxalase I and glutathione levels and lower glutathione peroxidase activity. A depleted level of total glutathione and of glyoxalase I for specimens of water plant 2 (for both experimental times), without correlation with the distances in the pipeline, suggests that river plant water can also lead to potentially adverse effects on selected biochemical parameters in C. carpio.     

Short- and medium-term effects of experimental nitrogen fertilization on arthropods associated with Calluna vulgaris heathlands in north-west Spain

We studied the short- and medium-term effects of experimental nitrogen fertilization (3 and 15 months after the treatment) on the arthropods of Calluna vulgaris heathlands in NW Spain. Three heathland sites were selected with two permanent plots per site: control and fertilized. Ammonium nitrate fertilizer (56 kg N ha(-1) yr(-1)) was applied monthly and insects were caught using pitfall traps. We found mainly species-level responses to nitrogen addition. Seven species (e.g. Lochmaea suturalis) showed a consistent trend (benefited or harmed) in both periods and were proposed as possible reliable indicators of the effects of nitrogen deposition in these ecosystems. We also found variable arthropod trophic-group responses: (a) herbivores (leaf beetles, true bugs) increased in abundance on a short-term scale; (b) predators (carabid beetles, true bugs) showed opposite and less clear responses in both periods. Further long-term studies are needed to determine the mechanisms underlying the observed arthropod responses.     

Characterizing effects of uncertainties in MSW composting process through a coupled fuzzy vertex and factorial-analysis approach

A coupled fuzzy vertex and factorial-analysis approach was developed in this study for systematically characterizing effects of uncertainties in a municipal solid waste composting process. A comprehensive composting process model was also embedded into the system framework and used to address substrate decomposition and biomass growth, as well as the interactions between moisture contents, temperatures, and oxygen concentrations. The applicability of the proposed method was verified through a custom-made pilot-scale composting system. Results from fuzzy simulation indicated that the fuzzy vertex method could effectively communicate implicit knowledge into dynamic simulations and thus provide valuable information for enhancing composting process control under uncertainty. The factorial analysis was effective in quantifying the proportion to which the uncertainty of each single or interactive effect of model parameters contributes to the overall uncertainty of the system outcomes. Thus, sensitive parameters that may lead to errors or unreasonable predictions can be determined. The proposed study system could not only be used in characterizing combined effects of uncertainties for composting processes, but was also applicable to many other environmental modelling systems.