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The vadose zone is a reservoir for geogenic and anthropogenic contaminants. Nitrogen and water infiltration can affect biogeochemical processes in this zone, ultimately affecting groundwater quality. In this large-scale field study, we evaluated the input and occurrence of water and nitrogen species in the vadose zone of a public water supply wellhead protection (WHP) area (defined by a 50-year travel time to groundwater for public supply wells) and potential transport of nitrate, ammonium, arsenic, and uranium. Thirty-two deep cores were collected and grouped by irrigation practices: pivot (n = 20), gravity (n = 4) irrigated using groundwater, and non-irrigated (n = 8) sites. Beneath pivot-irrigated sites, sediment nitrate concentrations were significantly (p < 0.05) lower, while ammonium concentrations were significantly (p < 0.05) higher than under gravity sites. The spatial distribution of sediment arsenic and uranium was evaluated against estimated nitrogen and water loading beneath cropland. Irrigation practices were randomly distributed throughout the WHP area and presented a contrasting pattern of sediment arsenic and uranium occurrence. Sediment arsenic correlated with iron (r = 0.32, p < 0.05), uranium negatively correlated to sediment nitrate (r = -0.23, p < 0.05), and ammonium (r = -0.19 p < 0.05). This study reveals that irrigation water and nitrogen influx influence vadose zone geochemistry and mobilization of geogenic contaminants affecting groundwater quality beneath intensive agricultural systems., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Extreme climate events including heat waves and droughts are projected to become more frequent under future climate change conditions. However, the mechanisms between soybean yields and climate factors, specifically involving variable rainfall and high heat episodes, are still unclear, particularly with respect to spatial trends in the United States (US) Midwest. A recently modified version of the model GLYCIM was used to evaluate rainfed soybean production across 12 states at a 10 km spatial resolution for three time periods (2011-2020, 2051-2060, 2091-2099) under Representative Concentration Pathway (RCP) scenarios 4.5 and 8.5. Results showed that except for the northernmost Midwest counties, most of the current rainfed cropping system in the Midwest would suffer a 24.6-47.4 % yield loss without considering the CO 2 fertility effect. Incorporating the effect of elevated CO 2 showed a smaller yield loss of 11.6-29.5 %. The increased frequency of extreme degree days (EDD) or accumulation of hourly temperatures above 30 °C associated with increased vapor pressure deficit (VPD) played a key role in contributing to water deficits and resultant crop losses under these future climate conditions. Although a relatively weak relationship between summer rainfall and crop yield was observed, decreased rainfall caused VPD to increase which induced crop water deficits. These findings suggest that it is crucial to consider VPD along with high temperature and low rainfall trends simultaneously for development of potential management or breeding-based adaptative strategies for soybean., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

GOSSYM, a mechanistic, process-level cotton crop simulation model, has a two-dimensional (2D) gridded soil model called Rhizos that simulates the below-ground processes daily. Water movement is based on gradients of water content and not hydraulic heads. In GOSSYM, photosynthesis is calculated using a daily empirical light response function that requires calibration for response to elevated carbon dioxide (CO 2 ). This report discusses improvements made to the GOSSYM model for soil, photosynthesis, and transpiration processes. GOSSYM's predictions of below-ground processes using Rhizos are improved by replacing it with 2DSOIL, a mechanistic 2D finite element soil process model. The photosynthesis and transpiration model in GOSSYM is replaced with a Farquhar biochemical model and Ball-Berry leaf energy balance model. The newly developed model (modified GOSSYM) is evaluated using field-scale and experimental data from SPAR (soil-plant-atmosphere-research) chambers. Modified GOSSYM better predicted net photosynthesis (root mean square error (RMSE) 25.5 versus 45.2 g CO 2  m -2  day -1 ; index of agreement (IA) 0.89 versus 0.76) and transpiration (RMSE 3.3 versus 13.7 L m -2  day -1 ; IA 0.92 versus 0.14) and improved the yield prediction by 6.0%. Modified GOSSYM improved the simulation of soil, photosynthesis, and transpiration processes, thereby improving the predictive ability of cotton crop growth and development., (© 2023. The Author(s).)

The movement of nitrate to surface water bodies during snow accumulation and melting has been extensively studied, but there are only limited studies on the influence of snow processes on nitrate leaching to groundwater. The present study investigated the impact of snow processes on nitrate leaching to groundwater based on a simulation modeling approach using HYDRUS-1D. HYDRUS-1D model has a temperature threshold-based snow model in addition to water, solute, and heat simulation components. The snow component in HYDRUS-1D was previously not applied to snow simulation studies since the method does not consider a detailed physical and process-based representation of snow accumulation and melting. In the present study, HYDRUS-1D was used to simulate snow accumulation and melting over 30 years for a location in Waverly, Lancaster County, Nebraska, USA. From the simulations, it was observed that the calibrated temperature threshold based snow module in HYDRUS-1D is effective in simulating snow accumulation and melting, as shown by the index of agreement and root mean squared error of 0.74 and 2.70 cm for calibration (15 years) and 0.88 and 2.70 cm for validation (15 years), respectively. The impact of snow melt on nitrate leaching was studied based on a study area with corn cultivation (Waverly, Nebraska, USA). A long-term (60 years) analysis was carried out for irrigated and non-irrigated agriculture with and without precipitation as snow. A higher nitrate leaching to groundwater was observed in the order of irrigated-with snow (54,038 kg/ha), irrigated-without snow (53,516 kg/ha), non-irrigated-with snow (7,431 kg/ha), and non-irrigated-without snow (7,090 kg/ha). This displays a 0.98% and 4.81% increase in nitrate leaching due to snow in irrigated and non-irrigated conditions, respectively. When extrapolated over the corn cultivated regions in Nebraska, this resulted in a difference of 1.2E+09 kg and 6.1E+08 kg of nitrate when considering snow in irrigated and non-irrigated areas over 60 years. This is the first study that has analyzed the long-term impact of snow on nitrate transport to groundwater based on a simulation modeling approach. The results show that snow accumulation and melting plays a vital role in the nitrate leaching into the groundwater and indicates the importance of considering snow components in similar studies., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

Groundwater overuse in different domains will eventually lead to global freshwater scarcity. To meet the anticipated demands, many governments worldwide are employing innovative and traditional techniques for forecasting groundwater availability by conducting research and studies. One challenging step for this type of study is collecting groundwater data from different sites and securely sending it to the nearby edges without exposure to hacking and data tampering. In the current paper, we send raw data formats from the Internet of Things to the Distributed Data Storage (DDS) and Blockchain (BC) edges. We use a distributed and decentralized architecture to store the statistics, perform double hashing, and implement access control through smart contracts. This work demonstrates a modern and innovative approach combining DDS and BC technologies to overcome traditional data sharing, and centralized storage, while addressing blockchain limitations. We have shown performance improvements with increased data quality and integrity.

It is a known fact that large quantities of farm and meat products rot and are wasted if correct actions are not taken, which may lead to serious health issues if consumed. There is no proper system for tracking and communicating the status of the goods to their respective stakeholders in a secure way. Consumers have every right to know the quality of the products they consume. Using monitoring tools, such as the Internet of Agricultural Things (IoAT), and modern data protection techniques for storing and sharing, will help mitigate data integrity issues during the transmission of sensor records, increasing the data quality. The visibility state at the customer end is also improved, and they are aware of the agricultural product's conditions throughout the real-time distribution process. In this paper, we developed and implemented a CorDapp application to manage the data for the supply chain, called "agroString". We collected the temperature and humidity data using IoAT-Edge devices and various datasets from multiple sources. We then sent those readings to the CorDapp agroString and successfully shared them among the relevant parties. With the help of a Corda private blockchain, we attempted to increase data integrity, trust, visibility, provenance, and quality at each logistic step, while decreasing blockchain and central system limitations.

Improvement of nutrient use efficiency and limiting trace elements such as arsenic and uranium bioavailability is critical for sustainable agriculture and food safety. Arsenic and uranium possess different properties and mobility in soils, which complicates the effort to reduce their uptake by plants. Here, we postulate that unsaturated soil amended with ferrihydrite nanominerals leads to improved nutrient retention and helps reduce uptake of these geogenic contaminants. Unsaturated soil is primarily oxic and can provide a stable environment for ferrihydrite nanominerals. To demonstrate the utility of ferrihydrite soil amendment, maize was grown in an unsaturated agricultural soil that is known to contain geogenic arsenic and uranium. The soil was maintained at a gravimetric moisture content of 15.1 ± 2.5%, typical of periodically irrigated soils of the US Corn Belt. Synthetic 2-line ferrihydrite was used in low doses as a soil amendment at three levels (0.00% w/w (control), 0.05% w/w and 0.10% w/w). Further, the irrigation water was fortified (~50 μg L -1 each) with elevated arsenic and uranium levels. Plant dry biomass at maturity was ~13.5% higher than that grown in soil not receiving ferrihydrite, indicating positive impact of ferrihydrite on plant growth. Arsenic and uranium concentrations in maize crops (root, shoot and grain combined) were ~ 20% lower in amended soils than that in control soils. Our findings suggest that the addition of low doses of iron nanomineral soil amendment can positively influence rhizosphere geochemical processes, enhancing nutrient plant availability and reduce trace contaminants plant uptake in sprinkler irrigated agroecosystem, which is 55% of total irrigated area in the United States., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interest or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier B.V. All rights reserved.)

Nanomaterials (NMs), both natural and synthetic, are produced, transformed, and exported into our environment daily. Natural NMs annual flux to the environment is around 97% of the total and is significantly higher than synthetic NMs. However, synthetic NMs are considered to have a detrimental effect on the environment. The extensive usage of synthetic NMs in different fields, including chemical, engineering, electronics, and medicine, makes them susceptible to be discharged into the atmosphere, various water sources, soil, and landfill waste. As ever-larger quantities of NMs end up in our environment and start interacting with the biota, it is crucial to understand their behavior under various environmental conditions, their exposure pathway, and their health effects on human beings. This review paper comprises a large portion of the latest research on NMs and the environment. The article describes the natural and synthetic NMs, covering both incidental and engineered NMs and their behavior in the natural environment. The review includes a brief discussion on sampling strategies and various analytical tools to study NMs in complex environmental matrices. The interaction of NMs in natural environments and their pathway to human exposure has been summarized. The potential of NMs to impact human health has been elaborated. The nanotoxicological effect of NMs based on their inherent properties concerning to human health is also reviewed. The knowledge gaps and future research needs on NMs are reported. The findings in this paper will be a resource for researchers working on NMs all over the world to understand better the challenges associated with NMs in the natural environment and their human health effects., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

To meet global health and sanitation goals, there is a continued need for sustainable wastewater treatment alternatives that require minimal energy and investment. Vermifiltration, a technology gaining relevance in Africa and Asia, may be an alternative to traditional wastewater treatment systems due to its cost-effectiveness, ease of application and maintenance, and sustainability. However, nitrogen removal in vermifiltration is not well understood since most of the prior research focuses on organics removal. Thus, a state of the art review is necessary to separately focus on the mechanisms associated with nitrogen removal in vermifiltration, along with the factors affecting nitrogen removal. For the first time, this review attempts to present the types of vermifilter based on their flow pattern. The review further discusses the current status of the application of vermifiltration, along with the benefits and limitations associated with the adoption of this technology. It also explores possible strategies that could be adopted to maximize the nitrogen removal potential of vermifilters as optimizing nitrogen removal is critical for improving the performance of vermifiltration based treatment systems., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

Contamination from pesticides and nitrate in groundwater is a significant threat to water quality in general and agriculturally intensive regions in particular. Three widely used machine learning models, namely, artificial neural networks (ANN), support vector machines (SVM), and extreme gradient boosting (XGB), were evaluated for their efficacy in predicting contamination levels using sparse data with non-linear relationships. The predictive ability of the models was assessed using a dataset consisting of 303 wells across 12 Midwestern states in the USA. Multiple hydrogeologic, water quality, and land use features were chosen as the independent variables, and classes were based on measured concentration ranges of nitrate and pesticide. This study evaluates the classification performance of the models for two, three, and four class scenarios and compares them with the corresponding regression models. The study also examines the issue of class imbalance and tests the efficacy of three class imbalance mitigation techniques: oversampling, weighting, and oversampling and weighting, for all the scenarios. The models' performance is reported using multiple metrics, both insensitive to class imbalance (accuracy) and sensitive to class imbalance (F1 score and MCC). Finally, the study assesses the importance of features using game-theoretic Shapley values to rank features consistently and offer model interpretability.

Redox driven mobilization and plant uptake of contaminants under transiently saturated soil conditions need to be clarified to ensure food and water quality across different irrigation systems. We postulate that solid-phase iron reduction in anoxic microsites present in the rhizosphere of unsaturated soil is a key driver for mobilization and bioavailability of contaminants under nonflooded irrigation. To clarify this, two major crops, corn and soybean differing in iron uptake strategies, were grown in irrigated synthetic soil under semiarid conditions with gravimetric moisture content ∼12.5 ± 2.4%. 2-line ferrihydrite, which was coprecipitated with uranium and arsenic, served as the only iron source in soil. Irrespective of crop type, reduced iron was detected in pore water and postexperiment rhizosphere soil confirming ferrihydrite reduction. These results support the presence of localized anoxic microsites in the otherwise aerobic porous bulk soil causing reduction of ferrihydrite and concomitant increase in plant uptake of comobilized contaminants. Our findings indicate that reactive iron minerals undergo reductive dissolution inside anoxic microsites of primarily unsaturated soil, which may have implications on the mobility of trace element contaminants such as arsenic and uranium in irrigated unsaturated soils, accounting for 55% of the irrigated area in the US.

Global demand for livestock products is rising, resulting in a growing demand for feed and potentially burdening freshwater resources to produce this feed. To offset this increased pressure on water resources, the environmental performance of livestock sector should continue to improve. Over the last few decades, product output per animal and feedstuff yields in the US have improved, but before now it was unclear to what extent these improvements influenced the water productivity (WP) of the livestock products. In this research, we estimate changes in WP of animal products from 1960 to 2016. We consider feed conversion ratios (dry matter intake per head divided by product output per head), feed composition per animal category, and estimated the water footprint of livestock production following the Water Footprint Network's Water Footprint Assessment methodology. The current WP of all livestock products appears to be much better than in 1960. The observed improvements in WPs are due to a number of factors, including increases in livestock productivity, feed conversion ratios and feed crop yields, the latter one reducing the water footprint of feed inputs. Monogastric animals (poultry and swine) have a high feed-use efficiency compared to ruminants (cattle), but ruminants consume relatively large portion of feed that is non-edible for humans. Per unit of energy content, milk has the largest WP followed by chicken and pork. Per gram of protein, poultry products (chicken meat, egg and turkey meat) have the largest WP, followed by cattle milk and pork. Beef has the smallest WP. These data provide important information that may aid the development of strategies to improve WP of the livestock sector., (Copyright © 2019 The Authors. Published by Elsevier Ltd.. All rights reserved.)

The impact of commonly-used livestock antibiotics on soil nitrogen transformations under varying redox conditions is largely unknown. Soil column incubations were conducted using three livestock antibiotics (monensin, lincomycin and sulfamethazine) to better understand the fate of the antibiotics, their effect on nitrogen transformation, and their impact on soil microbial communities under aerobic, anoxic, and denitrifying conditions. While monensin was not recovered in the effluent, lincomycin and sulfamethazine concentrations decreased slightly during transport through the columns. Sorption, and to a limited extent degradation, are likely to be the primary processes leading to antibiotic attenuation during leaching. Antibiotics also affected microbial respiration and clearly impacted nitrogen transformation. The occurrence of the three antibiotics as a mixture, as well as the occurrence of lincomycin alone affected, by inhibiting any nitrite reduction, the denitrification process. Discontinuing antibiotics additions restored microbial denitrification. Metagenomic analysis indicated that Proteobacteria, Bacteroidetes, Actinobacteria, and Chloroflexi were the predominant phyla observed throughout the study. Results suggested that episodic occurrence of antibiotics led to a temporal change in microbial community composition in the upper portion of the columns while only transient changes occurred in the lower portion. Thus, the occurrence of high concentrations of veterinary antibiotic residues could impact nitrogen cycling in soils receiving wastewater runoff or manure applications with potential longer-term microbial community changes possible at higher antibiotic concentrations., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

A four-decade dataset (1974-2013) of 107,823 nitrate samples in 25,993 wells from western and eastern parts of Nebraska was used to assess long-term trends of groundwater nitrate concentration and decadal changes in the extent of groundwater nitrate-contaminated areas (NO 3 -N ≥ 10 mg N/L) over the entire state. Spatial statistics and regressions were used to investigate the relationships between groundwater nitrate concentrations and several potential natural and anthropogenic factors, including soil drainage capacities, vadose zone characteristics, crop production areas, and irrigation systems. The results of this study show that there is no statistically significant trend in groundwater nitrate concentrations in western Nebraska, in contrast with the increasing trend (p < .05) to the east. The spatial extent and nitrate concentrations in contaminated groundwater in center pivot-irrigated areas was less than in gravity-irrigated areas. Areas with a thicker vadose zone and larger saturated thickness of the aquifer have relatively lower nitrate concentrations. The results of a classification and regression tree (CART) model indicate the difference in the influence of physical factors on groundwater nitrate concentrations between western and eastern Nebraska, namely that groundwater nitrate concentrations correspond with vadose zone thickness, effective hydraulic conductivity, and saturated thickness in the west, while in eastern Nebraska, concentrations are correlated with average percent sand in the topsoil (0-150 cm), well depth, and effective hydraulic conductivity., (Copyright © 2019 The Authors. Published by Elsevier B.V. All rights reserved.)

Driven by biofuel policies, which aim to reduce greenhouse gas (GHG) emissions and increase domestic energy supply, global production and consumption of bioethanol have doubled between 2007 and 2016, with rapid growth in corn-based bioethanol in the U.S. and sugar cane-based bioethanol in Brazil. Advances in crop yields, energy use efficiency in fertilizer production, biomass-to-ethanol conversion rates, and energy efficiency in ethanol production have improved the energy balance and GHG emission reduction potential of bioethanol. In the current study, the water, energy, and carbon footprints of bioethanol from corn in the U.S. and sugar cane in Brazil were assessed. The results show that U.S. corn bioethanol has a smaller water footprint (541 L water/L bioethanol) than Brazilian sugar cane bioethanol (1115 L water/L bioethanol). Brazilian sugar cane bioethanol has, however, a better energy balance (17.7 MJ/L bioethanol) and smaller carbon footprint (38.5 g CO 2 e/MJ) than U.S. bioethanol, which has an energy balance of 11.2 MJ/L bioethanol and carbon footprint of 44.9 g CO 2 e/MJ. The results show regional differences in the three footprints and highlight the need to take these differences into consideration to understand the implications of biofuel production for local water resources, net energy production, and climate change mitigation.

The occurrence of pharmaceutical and steroid compounds in groundwater due to wastewater reuse has been reported and is of concern in tropical islands which primarily rely on groundwater. The objective of this study was to investigate the occurrence and removal of 43 pharmaceutical and steroid compounds detected in wastewater at four different wastewater treatment plants (WWTPs) in Hawai'i and to understand their environmental behavior through tropical soils as the treated effluents are used in landscapes for irrigation. Eight soil sampling locations, collected at three different depths, representing the most common soil types in Hawai'i and four WWTPs located across the major Hawaiian Islands were used. Disturbed soil samples were used to conduct the soil sorption and degradation studies and to estimate the leaching risk associated to the identified compounds. Quantification of selected compounds was conducted using liquid chromatography-tandem mass spectrometry (LC-MS/MS). Among the investigated compounds, only ten were detected in the treated effluents at concentrations ranging from 0.004 to 0.900 μg L -1 . Caffeine (64 μg L -1 ) and ibuprofen (96.5 μg L -1 ) showed the highest concentration in raw samples, while diphenhydramine (0.9 μg L -1 ) showed the highest concentration in treated effluent samples. Sulfamethoxazole showed the lowest removal (0-75%). Several pharmaceuticals showed consistently higher sorption capacity and longer persistency compared with steroids regardless of soil types and depths. Poamoho (Oxisol soil) and Waimānalo (Mollisol soil) showed the highest sorption capacity, while Waimea (Entisol soil) showed the lowest sorption capacity. Soil physico-chemical properties (i.e., clay content, level of organic carbon, and presence of metal oxide) and soil depth highly impacted the sorption behavior of the selected pharmaceutical compounds. In particular, the sorption capacity decreased with soil depth due to the higher level of organic carbon present in the first 30 cm compared with the deeper depths (60-90 cm)., (Copyright © 2018 Elsevier B.V. All rights reserved.)

The anticoagulant rodenticides brodifacoum, chlorophacinone, and diphacinone have been proposed for broadcast application in some forested areas in Hawai'i to protect rare and endangered native bird species from introduced mice and rats. Groundwater resources in Hawai'i are prone to contamination due to the intrinsic aquifer vulnerability to leaching from the land surface. Because of the hydrogeologic complexity, Hawai'i uses a Tier-I leaching assessment tool, CLERS, to make registration decisions for new or existing chemicals. The CLERS tool uses soil and pesticide properties as well as water recharge through the soil profile in a GIS framework to estimate mass attenuation of the chemicals at a given depth and compares against this attenuation factor against those of a known leacher and a non-leacher. Disturbed soil samples were collected across the state of Hawai'i, including the islands of Hawai'i, Kaho'olawe, Kaua'i, Lana'i, Maui, Moloka'i, and O'ahu, with two sampling locations per island, except for Kaua'i which had three. As only limited information on chemical properties of these anticoagulants in soils is available, laboratory experiments were performed to determine the sorption capacity (K d ) and the degradation rate (T 1/2 ) of brodifacoum, chlorophacinone, and diphacinone to construct a proper chemical database. Depending on the soil type, T 1/2 values ranged between 37 and 248days for diphacinone, between 39 and 1000days for chlorophacinone, and between 72 and 462days for brodifacoum. These data were used in the CLERS tool to estimate leaching risks for these chemicals primarily in forested areas of the state where the chemicals are likely to be applied. The results from the CLERS tool indicate low risks of leaching of these three compounds into aquifers in five out of six major Hawaiian Islands. Diphacinone showed medium risk of leaching in a few remote areas in Maui., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Agricultural crops have a long history of being irrigated with recycled wastewater (RW). However, its use on vegetable crops has been of concern due to the potential prevalence of microcontaminants, such as pharmaceuticals and personal care products (PPCPs) in the latter, which represents a possible health hazard to consumers. We investigated the uptake of three PPCPs (atenolol, diclofenac, and ofloxacin), at three different concentrations in irrigation water (0.5, 5, and 25 μg L -1 ) in relation to three varying volumetric soil moisture depletion levels of 14 % (-4.26 kPa), 10 % (-8.66 kPa), and 7 % (-18.37 kPa) by various vegetable crop species. Experiments were conducted in a split-split block completely randomized design. PPCPs were extracted using a developed method of accelerated solvent extraction and solid phase extraction and analyzed via liquid chromatography mass spectrometry (LCMS). Results indicate that all treated crops were capable of PPCP uptake at nanogram per gram concentrations independent of the applied soil moisture depletion levels and PPCP concentrations. Ofloxacin was the chemical with the highest uptake amounts, followed by atenolol and then diclofenac. Although the results were not statistically significant, higher concentrations of PPCPs were detected in plants maintained under higher soil moisture levels of 14 % (-4.26 kPa).

Water Productivity (WP) of a crop defines the relationship between the economic or physical yield of the crop and its water use. With this concept it is possible to identify disproportionate water use or water-limited yield gaps and thereby support improvements in agricultural water management. However, too often important qualitative and quantitative environmental factors are not part of a WP analysis and therefore neglect the aspect of maintaining a sustainable agricultural system. In this study, we examine both the physical and economic WP in perspective with temporally changing environmental conditions. The physical WP analysis was performed by comparing simulated maximum attainable corn yields per unit of water using the crop model Hybrid-Maize with observed data from 2005 through 2013 from 108 farm plots in the Central Platte and the Tri Basin Natural Resource Districts of Nebraska. In order to expand the WP analysis on external factors influencing yields, a second model, Maize-N, was used to estimate optimal nitrogen (N)-fertilizer rate for specific fields in the study area. Finally, a vadose zone flow and transport model, HYDRUS-1D for simulating vertical nutrient transport in the soil, was used to estimate locations of nitrogen pulses in the soil profile. The comparison of simulated and observed data revealed that WP was not on an optimal level, mainly due to large amounts of irrigation used in the study area. The further analysis illustrated year-to-year variations of WP during the nine consecutive years, as well as the need to improve fertilizer management to favor WP and environmental quality. In addition, we addressed the negative influence of groundwater depletion on the economic WP through increasing pumping costs. In summary, this study demonstrated that involving temporal variations of WP as well as associated environmental and economic issues can represent a bigger picture of WP that can help to create incentives to sustainably improve agricultural production., Competing Interests: The authors have declared that no competing interests exist.

On the Hawaiian Islands, groundwater is the principal source of potable water and contamination of this key resource by pesticides is of great concern. To evaluate the leaching potential of four weak acid herbicides [aminocyclopyrachlor, picloram, metsulfuron-methyl, biologically active diketonitrile degradate of isoxaflutole (DKN)] and two neutral non-ionizable herbicides [oxyfluorfen, alachlor], their sorption coefficients were determined on three prevalent soils from the island of Oahu. Metsulfuron-methyl, aminocylcopyrachlor, picloram, and DKN were relatively low sorbing herbicides (K(oc) = 3-53 mL g(-1)), alachlor was intermediate (K(oc) = 120-150 mL g(-1)), and oxyfluorfen sorbed very strongly to the three soils (K(oc) > 12,000 mL g(-1)). Following determination of K(oc) values, the groundwater ubiquity score (GUS) indices for these compounds were calculated to predicted their behavior with the Comprehensive Leaching Risk Assessment System (CLEARS; Tier-1 methodology for Hawaii). Metsulfuron-methyl, aminocyclopyrachlor, picloram, and DKN would be categorized as likely leachers in all three Hawaiian soils, indicating a high risk of groundwater contamination across the island of Oahu. In contrast, oxyfluorfen, regardless of the degradation rate, would possess a low and acceptable leaching risk due to its high sorption on all three soils. The leaching potential of alachlor was more difficult to classify, with a GUS value between 1.8 and 2.8. In addition, four different biochar amendments to these soils did not significantly alter their sorption capacities for aminocyclopyrachlor, indicating a relatively low impact of black carbon additions from geologic volcanic inputs of black carbon. Due to the fact that pesticide environmental risks are chiefly dependent on local soil characteristics, this work has demonstrated that once soil specific sorption parameters are known one can assess the potential pesticide leaching risks., (Published by Elsevier Ltd.)

Slow sand filtration (SSF) has been widely used as a means of providing potable water due to its efficacy, low cost, and minimal maintenance. Advances in analytical instrumentation have revealed the occurrence of pharmaceutically active compounds (PhACs) in surface water as well as in groundwater. It is unclear if the presence of these compounds in the feed water can interfere with the performances of an SSF unit. The aim of this work was to examine i) the ability of two SSF units to remove six PhACs (caffeine, carbamazepine, 17-β estradiol [E2], estrone [E1], gemfibrozil, and phenazone), and ii) the impact of these PhACs on the removal of bacteria by two SSF units. The presence of PhACs in feed water for SSF can occur in surface waters impacted by wastewater or leakage from sewers and septic tanks, as well as in developing countries where unregulated use and improper disposal are prevalent. Two pilot-scale SSF units were used during the study. Unit B1 was fed with stream water with 1% of primary effluent added, while unit B2 was fed with stream water alone. Although limited removal (<10%) of carbamazepine, gemfibrozil, and phenazone occurred, the complete removal of caffeine, and the partial removal (11-92%) of E2 and E1 were observed in the two SSF units. The results of this study suggest that the occurrence of the selected PhACs, probably estrogens and caffeine, in the feed water at 50 μg L(-1) affected the ability of the schmutzdecke to remove total coliform and Escherichia coli. The bacterial removal achieved within the schmutzdecke dropped from 95% to less than 20% by the end of the study. This decrease in removal may be related to the change in the microbial community within the schmutzdecke. A diverse microbial community, including Bacteroidetes and several classes of Proteobacteria, was replaced by a microbial community in which Gammaproteobacteria was the predominant phylum (99%). Despite the low removal achieved within the schmutzdecke, removal of total coliform and E. coli greater than 99% occurred after both SSF units throughout the study. Bacterial removal occurred in the upper half of the sand filter. This was probably due to a diverse microbial community established in the packing material, in which Bacteroidetes (13-25%), Acidobacteria (7-17%) and several classes of Proteobacteria (35-52%) (Alpha-, Beta-, Delta-, and Gammaproteobacteria) were the predominant phyla., (Copyright © 2015 Elsevier B.V. All rights reserved.)

A large-scale leaching assessment tool not only illustrates soil (or groundwater) vulnerability in unmonitored areas, but also can identify areas of potential concern for agrochemical contamination. This study describes the methodology of how the statewide leaching tool in Hawaii modified recently for use with pesticides and volatile organic compounds can be extended to the national assessment of soil vulnerability ratings. For this study, the tool was updated by extending the soil and recharge maps to cover the lower 48 states in the United States (US). In addition, digital maps of annual pesticide use (at a national scale) as well as detailed soil properties and monthly recharge rates (at high spatial and temporal resolutions) were used to examine variations in the leaching (loads) of pesticides for the upper soil horizons. Results showed that the extended tool successfully delineated areas of high to low vulnerability to selected pesticides. The leaching potential was high for picloram, medium for simazine, and low to negligible for 2,4-D and glyphosate. The mass loadings of picloram moving below 0.5 m depth increased greatly in northwestern and central US that recorded its extensive use in agricultural crops. However, in addition to the amount of pesticide used, annual leaching load of atrazine was also affected by other factors that determined the intrinsic aquifer vulnerability such as soil and recharge properties. Spatial and temporal resolutions of digital maps had a great effect on the leaching potential of pesticides, requiring a trade-off between data availability and accuracy. Potential applications of this tool include the rapid, large-scale vulnerability assessments for emerging contaminants which are hard to quantify directly through vadose zone models due to lack of full environmental data., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

The fate of pesticides in tropical soils is still not understood as well as it is for soils in temperate regions. In this study, water flow and transport of bromide tracer and five pesticides (atrazine, imazaquin, sulfometuron methyl, S-metolachlor, and imidacloprid) through an undisturbed soil column of tropical Oxisol were analyzed using a one-dimensional numerical model. The numerical model is based on Richards' equation for solving water flow, and the advection-dispersion equation for solving solute transport. Data from a laboratory column leaching experiment were used in the uncertainty analysis using a global optimization methodology to evaluate the model's sensitivity to transport parameters. All pesticides were found to be relatively mobile (sorption distribution coefficients lower than 2 cm(3) g(-1)). Experimental data indicated significant non-conservative behavior of bromide tracer. All pesticides, with the exception of imidacloprid, were found less persistent (degradation half-lives smaller than 45 days). Three of the five pesticides (atrazine, sulfometuron methyl, and S-metolachlor) were better described by the linear kinetic sorption model, while the breakthrough curves of imazaquin and imidacloprid were more appropriately approximated using nonlinear instantaneous sorption. Sensitivity analysis suggested that the model is most sensitive to sorption distribution coefficient. The prediction limits contained most of the measured points of the experimental breakthrough curves, indicating adequate model concept and model structure for the description of transport processes in the soil column under study. Uncertainty analysis using a physically-based Monte Carlo modeling of pesticide fate and transport provides useful information for the evaluation of chemical leaching in Hawaii soils., (Copyright © 2015 Elsevier B.V. All rights reserved.)

The objective of this study was to investigate the effect of temperature, oxygen, and organic matter on the removal of selected pharmaceutically active compounds (PhACs) during simulated riverbank filtration (RBF). The behavior of six PhACs (caffeine, carbamazepine, 17-β estradiol [E2], estrone [E1], gemfibrozil, and phenazone) was evaluated by small flow-through column experiments. Results from our study showed that RBF can be used to treat many of the PhACs found in environmental waters. Local conditions at the RBF site, however, can affect the removal of PhACs and should be investigated. Biodegradation and sorption represented the predominant mechanisms involved during the removal of the selected PhACs. All selected PhACs showed limited and slower removal during the winter. Phenazone was highly impacted by the level of oxygen; complete depletion of phenazone below the analytical limit occurred only under aerobic conditions (dissolved oxygen >8 mg L(-1)). Caffeine and E2 were highly impacted by the presence of humic acid in the feed water. Caffeine and E2 were depleted below the detection limit in the presence of humic acid regardless of the temperature and the level of oxygen. E1 was impacted by the different environmental conditions and depletion below the detection limit occurred only during the summer under aerobic conditions. Carbamazepine (10%) and gemfibrozil (<30%) showed limited removal regardless of the different levels of temperature, oxygen and humic acid., (Copyright © 2014 Elsevier B.V. All rights reserved.)

The fate and transport of estrogen compounds in the environment is of increasing concern due to their potential impact on freshwater organisms, ecosystems and human health. The behavior of these compounds in batch experiments suggests low mobility, while field studies indicate the persistence of estrogen compounds in the soil with the possibility of migration to surface water as well as groundwater. To better understand the movement of these chemicals through soils, we examined their transport in three different Hawaiian soils and two aqueous matrices. The three different soils used were an Oxisol, a Mollisol and a cinder, characterized by different mineralogical properties and collected at depths of 60-90 cm and 210-240 cm. Two liquid matrices were used; deionized (DI) water containing calcium chloride (CaCl2), and recycled water collected from a wastewater treatment facility. The experiments were conducted in packed and structured columns. Non-equilibrium conditions were observed during the study, especially in the structured soil. This is believed to be primarily related to the presence of macropores in the soil. The presence of macropores resulted in reduced contact time between soil and estrogens, which facilitated their transport. We found that the organic carbon content and mineralogical composition of the soils had a profound effect on the transport of the estrogens. The mobility of estrone (E1) and 17β-estradiol (E2) was greater in cinder than in the other soils. In column experiments with recycled water, earlier breakthrough peaks and longer tails of estrogens were produced compared to those observed using DI water. The use of recycled water for agricultural purposes and the siting of septic tanks and cesspools should be critically reviewed in light of these findings, especially in areas where groundwater is the primary source of potable water, such as Hawaii., (Copyright © 2014 Elsevier B.V. All rights reserved.)

Determining optimal locations for best management practices (BMPs), including their field considerations and limitations, plays an important role for effective stormwater management. However, these issues have been often overlooked in modeling studies that focused on downstream water quality benefits. This study illustrates the methodology of locating infiltration trenches at suitable locations from spatial overlay analyses which combine multiple layers that address different aspects of field application into a composite map. Using seven thematic layers for each analysis, fuzzy logic was employed to develop a site suitability map for infiltration trenches, whereas the DRASTIC method was used to produce a groundwater vulnerability map on the island of Oahu, Hawaii, USA. In addition, the analytic hierarchy process (AHP), one of the most popular overlay analyses, was used for comparison to fuzzy logic. The results showed that the AHP and fuzzy logic methods developed significantly different index maps in terms of best locations and suitability scores. Specifically, the AHP method provided a maximum level of site suitability due to its inherent aggregation approach of all input layers in a linear equation. The most eligible areas in locating infiltration trenches were determined from the superposition of the site suitability and groundwater vulnerability maps using the fuzzy AND operator. The resulting map successfully balanced qualification criteria for a low risk of groundwater contamination and the best BMP site selection. The results of the sensitivity analysis showed that the suitability scores were strongly affected by the algorithms embedded in fuzzy logic; therefore, caution is recommended with their use in overlay analysis. Accordingly, this study demonstrates that the fuzzy logic analysis can not only be used to improve spatial decision quality along with other overlay approaches, but also is combined with general water quality models for initial and refined searches for the best locations of BMPs at the sub-basin level., (Copyright © 2014. Published by Elsevier B.V.)

Former sugarcane lands on the Island of Hawaii have elevated levels of soil arsenic (As) from historical use of arsenical pesticides. The bioaccessible fraction of total As (AsTOT), a measure of the potential for human As uptake by incidental ingestion of soil, is used in the assessment of human health risk and the determination of the need for remedial action. Ferric chloride plus lime and ferrous sulfate plus lime were applied to As-contaminated soils in a field plot setting to determine the potential for reducing in vitro bioaccessible As (AsIVBA) by increasing As sequestration by the formation of additional iron (Fe) oxyhydroxides. The two Fe sources performed similarly in reducing AsIVBA over a 2-year observation period, with 30-41% reduction in AsIVBA for 0.25wt% Fe dosing (dry soil basis) and 59-63% reduction for 0.5wt% Fe dosing. Addition of phosphate (PO4) to treated and untreated soils caused a significant increase in AsIVBA. Iron-treated and control soils showed more than twice the AsIVBA after the addition of 1500mgPkg(-1). The cost of in situ treatment of As-contaminated soil with ferrous sulfate plus lime to lower AsIVBA was estimated to be an order of magnitude less than excavation and landfill disposal on the Island of Hawaii, making the technology a viable alternative when remedial action objectives were based on AsIVBA levels., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We examined the mobility of 2-amino-4,6-dinitrobenzoic acid (2-A-4,6-DBA) a common photodegradation product of TNT, in soil taken from a former military training area on Oahu Island, Hawaii, USA. 2-A-4,6-DBA is stable and polar and has the potential to migrate to groundwater. Little experimentation has been conducted on explosives in tropical soils which differ chemically from soils in temperate climates. 2,4,6-Trinitrotoluene (TNT) and 1,3,5-hexahydro-1,3,5-trinitrotriazine (RDX) are the most commonly used secondary military explosives. Composition B (Comp B) is a frequently used 59/40/1 combination of RDX, TNT, and wax binder. In order to examine the effect of the presence of Comp B and its degradation products on the mobility of 2-A-4,6-DBA in soil, we dissolved field-collected Comp B fragments in water, exposed the solution to light and pumped it through soil and sand-packed stainless steel columns under abiotic saturated conditions. We found that in the presence of a complex mixture of explosives and degradation products, 2-A-4,6-DBA migrated faster than the parent compound (TNT) and other degradation products through both tropical soil and Ottawa sand (used as a reference) under sterile saturated conditions. The relatively rapid movement of 2-A-4,6-DBA suggests that it has the potential to contaminate underlying groundwater. However, the amount of 2-A-4,6-DBA produced under field conditions and its rate of biotic degradation were not part of this research, therefore, it is unknown how these factors might affect the transport and fate of 2-A-4,6-DBA., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Arsenical herbicides were used extensively for emergent weed control in Hawaiian sugar cane cultivation from 1913 to about 1950. As a result, surface soil arsenic concentrations average 280 mg kg(-1) across more than 60 km(2) of former sugar plantation land in the eastern portion of the Island of Hawaii. This study was conducted to elucidate the relationship between soil properties and arsenic bioaccessibility in the iron-rich volcanic soils. Soils are predominantly Andisols, formed by weathering of basaltic lava and tephra, with pedogenic solid phases consisting of short-range order iron oxyhydroxides, allophane-like aluminosilicates, and metal-humus compounds. These reactive solid phases strongly adsorb oxyanions, such as phosphate and arsenite/arsenate. High arsenic sorption capacity limits desorption and vertical migration within the soil column and prevents contamination of the underlying groundwater aquifer, despite high arsenic loading and precipitation rates. In vitro arsenic bioaccessibility, as measured by the SBRC gastric-phase test, ranges from 2% to 35% and averages 9% of total arsenic. Bioaccessible arsenic is higher in less weathered soils (Udifolists, Typic and Lithic Hydrudands) and lower in more weathered ash-dominant soils (Acrudoxic Hydrudands). Soil weathering indicators, such as reactive iron content, are strong predictors of arsenic bioaccessibility. Based on evidence from soil mineralogy, geochemistry and arsenic speciation, as well as limited soil arsenic bioavailability/bioaccessibility comparisons, risks to human health from direct contact (soil ingestion) are significantly reduced by low arsenic bioaccessibility. Nonetheless, some soils within former sugar cane cultivation areas contain bioaccessible arsenic concentrations exceeding Hawaii Department of Health risk-based action levels, and will require mitigating actions. Even higher levels of soil arsenic contamination have been identified at former pesticide storage and mixing areas, but are generally of localized extent., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Background: The behavior of the termiticide fipronil in soils was studied to assess its potential to contaminate ground and surface water. This study characterizes (1) adsorption of fipronil in three different soils, (2) transport of fipronil through leaching and runoff under simulated rainfall in these soils and (3) degradation of fipronil to fipronil sulfide and fipronil sulfone in these soils., Results: The adsorption experiments showed a Freundlich isotherm for fipronil with K(oc) equal to 1184 L kg(-1) . In the leaching experiments, the concentration of fipronil and its metabolites in leachate and runoff decreased asymptotically with time. The concentration of fipronil in the leachate from the three soils correlated inversely with soil organic carbon content. The degradation experiment showed that the half-life of fipronil in the soils ranged from 28 to 34 days when soil moisture content was 75% of field capacities, and that 10.7-23.5% of the degraded fipronil was transformed into the two metabolites (fipronil sulfide and fipronil sulfone)., Conclusion: Fipronil showed large losses through leaching but small losses via runoff owing to low volumes of runoff water generated and/or negligible particle-facilitated transport of fipronil. The half-life values of fipronil in all three soils were similar., (Copyright © 2011 Society of Chemical Industry.)

Transport of Cryptosporidium parvum oocysts and microspheres in two disparate (a clay- and Fe-rich, volcanic and a temperate, humic) agricultural soils were studied in the presence and absence of 100 mg L(-1) of sodium dodecyl benzene sulfonate (SDBS), and Suwannee River Humic Acid (SRHA) at pH 5.0-6.0. Transport of carboxylate-modified, 1.8 μm microspheres in soil columns was highly sensitive to the nature of the dissolved organic carbon (DOC), whereas oocysts transport was more affected by soil mineralogy. SDBS increased transport of microspheres from 48% to 87% through the tropical soil and from 43% to 93% in temperate soil. In contrast, SRHA reduced transport of microspheres from 48% to 28% in tropical soil and from 43% to 16% in temperate soil. SDBS also increased oocysts transport through the temperate soil 5-fold, whereas no oocyst transport was detected in tropical soil. SRHA had only a nominal effect in increasing oocysts transport in tropical soil, but caused a 6-fold increase in transport through the temperate soil. Amendments of only 4 mg L(-1) SRHA and SDBS decreased oocyst hydrophobicity from 66% to 20% and from 66% to 5%, respectively. However, SDBS increased microsphere hydrophobicity from 16% to 33%. Soil fines, which includes clays, and SRHA, both caused the oocysts zeta potential (ζ) to become more negative, but caused the highly hydrophilic microspheres to become less negatively charged. The disparate behaviors of the two colloids in the presence of an ionic surfactant and natural organic matter suggest that microspheres may not be suitable surrogates for oocysts in certain types of soils. These results indicate that whether or not DOC inhibits or promotes transport of oocysts and microspheres in agricultural soils and by how much, depends not only on the surface characteristics of the colloid, but the nature of the DOC and the soil mineralogy.

Background: Physically based tier-II models may serve as possible alternatives to expensive field and laboratory leaching experiments required for pesticide approval and registration. The objective of this study was to predict pesticide fate and transport at five different sites in Hawaii using data from an earlier field leaching experiment and a one-dimensional tier-II model. As the predicted concentration profiles of pesticides did not provide close agreement with data, inverse modeling was used to obtain adequate reactive transport parameters. The estimated transport parameters of pesticides were also utilized in a tier-I model, which is currently used by the state authorities to evaluate the relative leaching potential., Results: Water flow in soil profiles was simulated by the tier-II model with acceptable accuracy at all experimental sites. The observed concentration profiles and center of mass depths predicted by the tier-II simulations based on optimized transport parameters provided better agreements than did the non-optimized parameters. With optimized parameters, the tier-I model also delivered results consistent with observed pesticide center of mass depths., Conclusion: Tier-II numerical modeling helped to identify relevant transport processes in field leaching of pesticides. The process-based modeling of water flow and pesticide transport, coupled with the inverse procedure, can contribute significantly to the evaluation of chemical leaching in Hawaii soils., (Copyright © 2011 Society of Chemical Industry.)

Subsurface coherent structures and surface temperatures are investigated using simultaneous measurements of particle image velocimetry (PIV) and infrared (IR) thermography. Results for coherent structures from acoustic streaming and associated heating transfer in a rectangular tank with an acoustic horn mounted horizontally at the sidewall are presented. An observed vortex pair develops and propagates in the direction along the centerline of the horn. From the PIV velocity field data, distinct kinematic regions are found with the Lagrangian coherent structure (LCS) method. The implications of this analysis with respect to heat transfer and related sonochemical applications are discussed.

This study investigated the flux stability of select chemical and biological sewage markers, including caffeine, total nitrogen (TN), total suspended solids (TSS), E. coli, and enterococci, and their suitability in assessing the severity of rainfall-derived infiltration and inflow (RDII) in a residential sewershed. To quantify and compare marker flux stability, concentrations of the candidate markers in two dry-weather periods were determined and the one-day lag autocorrelation coefficients (r) of their mass fluxes were calculated. TN (r = 0.82-0.88) exhibited higher and more consistent flux stability than TSS (r = 0.49-0.82), caffeine (r = 0.56-0.58), E. coli (r = 0.36-0.87), and enterococci (by culture; r = 0.40-0.52), all of which except enterococci by qPCR (r = -0.10-0.21) showed significant autocorrelation. Sewage flows and marker concentrations were also monitored in two wet-weather periods, and the severity of RDII (R(RDII)) were calculated using either flow measurements or marker concentrations independently. Corresponding to its outstanding flux stability, R(RDII) values estimated by TN predicted all severe RDII instances and gave the highest and most consistent correlation (r = 0.74-0.78) among the different sewage markers. Overall, the study illustrated the feasibility of using the flux stability of sewage markers in assessing the severity of RDII and thereby deterioration levels in sewer systems.

Real-time measurements of acoustic streaming velocities and surface temperature fields using synchronized particle image velocimetry and infrared thermography are reported. Measurements were conducted using a 20 kHz Langevin type acoustic horn mounted vertically in a model sonochemical reactor of either degassed water or a glycerin-water mixture. These dissipative phenomena are found to be sensitive to small variations in the medium viscosity, and a correlation between the heat flux and vorticity was determined for unsteady convective heat transfer., (Copyright © 2011 Elsevier B.V. All rights reserved.)

The adsorption and degradation behavior of RDX, HMX, TNT and DNT and the impact of pH, ionic strength and dissolved organic matter on sorption were examined for two volcanic soils of a former military training area on Hawaii Island, Hawaii, USA. The transport of these chemicals in the soil was also studied in small packed columns and simulated using a water-flow and solute-transport model, HYDRUS&#95;1D. The results show that HMX and RDX are both significantly more mobile than TNT and DNT. The adsorbability of the four chemicals was ranked as: RDXRDX>DNT>TNT. No significant trend was observed for the effect of ionic strength, pH and dissolved organic carbon (DOC) on the adsorption of explosive compounds within the concentrations and pH ranges evaluated. The simulation results show that TNT and DNT would not leach beyond a depth of 30cm soil profile whereas a significant amount of HMX and RDX would pass the 30cm depth. It seems that the risk for contamination of groundwater is much higher for both HMX and RDX than for DNT and TNT as the substratum in this area consists of highly permeable lavas., (Copyright © 2010 Elsevier B.V. All rights reserved.)

In order to gain more information about the fate of Cryptosporidium parvum oocysts in tropical volcanic soils, the transport and attachment behaviors of oocysts and oocyst-sized polystyrene microspheres were studied in the presence of two soils. These soils were chosen because of their differing chemical and physical properties, i.e., an organic-rich (43-46% by mass) volcanic ash-derived soil from the island of Hawaii, and a red, iron (22-29% by mass), aluminum (29-45% by mass), and clay-rich (68-76% by mass) volcanic soil from the island of Oahu. A third agricultural soil, an organic- (13% by mass) and quartz-rich (40% by mass) soil from Illinois, was included for reference. In 10-cm long flow-through columns, oocysts and microspheres advecting through the red volcanic soil were almost completely (98% and 99%) immobilized. The modest breakthrough resulted from preferential flow-path structure inadvertently created by soil-particle aggregation during the re-wetting process. Although a high (99%) removal of oocysts and microsphere within the volcanic ash soil occurred initially, further examination revealed that transport was merely retarded because of highly reversible interactions with grain surfaces. Judging from the slope of the substantive and protracted tail of the breakthrough curve for the 1.8-μm microspheres, almost all (>99%) predictably would be recovered within ∼4000 pore volumes. This suggests that once contaminated, the volcanic ash soil could serve as a reservoir for subsequent contamination of groundwater, at least for pathogens of similar size or smaller. Because of the highly reversible nature of organic colloid immobilization in this soil type, C. parvum could contaminate surface water should overland flow during heavy precipitation events pick up near-surface grains to which they are attached. Surprisingly, oocyst and microsphere attachment to the reference soil from Illinois appeared to be at least as sensitive to changes in pH as was observed for the red, metal-oxide rich soil from Oahu. In contrast, colloidal attachment in the organic-rich, volcanic ash soil was relatively insensitive to changes in pH in spite of the high iron content. Given the fundamental differences in transport behavior of oocyst-sized colloids within the two volcanic soils of similar origin, agricultural practices modified to lessen C. parvum contamination of ground or surface water would necessitate taking the individual soil properties into account., (Copyright © 2010 Elsevier Ltd. All rights reserved.)

Background: Following the discovery of pesticides in wells, the Hawaii Department of Agriculture (HDOA) supported research to evaluate the likelihood of pesticide leaching to the groundwater in Hawaii. The aim of this study was to evaluate the relative leaching pattern of five pesticides at five different sites on three islands and to compare their leaching behavior with bromide and a reference chemical (atrazine) that is known to leach in Hawaiian conditions. Laboratory measurements of sorption and degradation of the pesticides were made., Results: Most of the applied mass of pesticides was still present in the top 80 cm after the 16 week study period. The aggregated oxisol at Kunia showed the most intensive leaching among the five sites. The revised attenuation factor screening approach used by the HDOA indicated that all chemicals, with the exception of trifloxystrobin, had the potential to leach. Similarly, the groundwater ubiquity score ranked trifloxystrobin as a non-leacher. The field leaching data, however, suggested that trifloxystrobin was the most mobile compound among the pesticides tested., Conclusion: Although the results were variable among the sites, the field and laboratory experiments provided useful information for regulating use of these pesticides in Hawaii.

Riverbank filtration (RBF) refers to the process of capturing surface water passing through the river-sediment-aquifer system by using a collection technique such as a well or an infiltration gallery. RBF removes nearly all suspended and a large number of dissolved contaminants from the surface water. Therefore, it can function as an effective pretreatment process in drinking-water production. TNT (2,4,6-trinitrotoluene), RDX (1,3,5-trinitro-1,3,5-triazacyclohexane), and HMX (1,3,5,7-tetranitro-1,3,5,7-tetrazocane) are three military explosive chemicals that are considered of concern to human health when present in source waters. This study is to evaluate the ability of the filtration media in RBF systems to remove these chemicals. The results from an anoxic batch test showed that all three chemicals will degrade while passing through streambed sediments. The pseudo first-order degradation-rate constants for TNT, RDX, and HMX were measured to be 0.33, 0.055, and 0.033d(-1), respectively. Under aerobic conditions only TNT showed significant degradation. Results from a model RBF system showed that the mobility of the three chemical contaminants in streambed sediments was in the order: HMX>RDX>TNT. The results suggest that RBF is capable of removing TNT and RDX but HMX levels may continue to be of concern-especially when collector wells use laterals running directly beneath the stream or riverbed.

Analytical methods for the determination of trifloxystrobin and four of its metabolites were developed in a leaching study conducted in Hawaii. To duplicate plots at each of five locations representing various agricultural areas in Hawaii, trifloxystrobin was applied at label rates and allowed to leach under normal rain and irrigation conditions. Soil samples were collected at weekly to monthly intervals and the residual concentrations of trifloxystrobin and metabolites measured. A quantitative analytical method for their determination in various soil samples was developed using accelerated solvent extraction (ASE), coupled with liquid chromatography-tandem mass spectrometry. Extraction solvent with various ratios of methanol to water, addition of EDTANa2 to the extract solvent, and ASE cell temperature were adjusted to improve recovery. Deuterated (E, E)-trifloxystrobin was chosen as the internal standard of the analytical method. The limit of quantitation was 2.5 ppb in the soil for trifloxystrobin and its metabolites. Laboratory aerobic degradation studies with the soils from the five sites were also conducted to measure the same compounds.

Laboratory column experiments were conducted to study the effects of anionic polyacrylamide (PAM) polymer and surfactant linear alkylbenzene sulfonate (LAS) on the movement of Escherichia coli and the FRNA phage MS-2. The study was designed to evaluate if PAM or PAM + LAS would enhance the mobility of human pathogens in tropical soils under unsaturated conditions. No breakthrough of phage was observed in a 10 cm column after passing 100 pore volumes of solution containing 1x10(8) plaque-forming units (PFU)/ml. In later experiments, after passing 10-20 pore volumes of influent containing 1x10(8)/ml MS-2 or E. coli through 15 cm columns, the soil was sliced and the organisms eluted. Phage moved slightly deeper in the polymer-treated column than in the control column. There was no measurable difference in the movement of E. coli in either polymer-treated or control columns. The properties of the soil (high amounts of metal oxides, kaolinitic clay), unsaturated flow conditions, and relatively high ionic strengths of the leaching solution attributed to significant retention of these indicators. The impacts of PAM and LAS on the mobility of E. coli or MS-2 phage in the chosen soils were not significant.

This paper describes an updated version of a screening tool for groundwater vulnerability assessment to evaluate pesticide leaching to groundwater, based on a revised version of the attenuation factor. The tool has been implemented in a geographical information system (GIS) covering the major islands of the state of Hawaii, USA. The Hawaii Department of Agriculture currently uses the tool in their pesticide evaluation process as a first-tier screening tool. The basic soil properties and pesticide properties necessary to compute the index, and estimates of their uncertainty, are included in the GIS. Uncertainties in soil and pesticide properties are accounted for using first-order uncertainty analysis. Classifications of pesticides as 'likely', 'uncertain' or 'unlikely' to leach are made on the basis of the uncertainty and a comparison of the revised attenuation factor with values and uncertainties of two reference chemicals. The reference chemicals represent what are considered to be a 'leachable' and a 'non-leachable' pesticide under Hawaii conditions. It is concluded that the tool is suitable for screening new and already used pesticides for the islands of Hawaii. However, the tool is associated with uncertainties that are not accounted for, so a conservative approach with respect to interpretation of the results and selection of pesticide parameters used in the tool is recommended.

In this study, a feed-forward back-propagation neural network (BPNN) was developed and applied to predict pesticide concentrations in groundwater monitoring wells. Pesticide concentration data are challenging to analyze because they tend to be highly censored. Input data to the neural network included the categorical indices of depth to aquifer material, pesticide leaching class, aquifer sensitivity to pesticide contamination, time (month) of sample collection, well depth, depth to water from land surface, and additional travel distance in the saturated zone (i.e., distance from land surface to midpoint of well screen). The output of the neural network was the total pesticide concentration detected in the well. The model prediction results produced good agreements with observed data in terms of correlation coefficient (R=0.87) and pesticide detection efficiency (E=89%), as well as good match between the observed and predicted "class" groups. The relative importance of input parameters to pesticide occurrence in groundwater was examined in terms of R, E, mean error (ME), root mean square error (RMSE), and pesticide occurrence "class" groups by eliminating some key input parameters to the model. Well depth and time of sample collection were the most sensitive input parameters for predicting the pesticide contamination potential of a well. This infers that wells tapping shallow aquifers are more vulnerable to pesticide contamination than those wells tapping deeper aquifers. Pesticide occurrences during post-application months (June through October) were found to be 2.5 to 3 times higher than pesticide occurrences during other months (November through April). The BPNN was used to rank the input parameters with highest potential to contaminate groundwater, including two original and five ancillary parameters. The two original parameters are depth to aquifer material and pesticide leaching class. When these two parameters were the only input parameters for the BPNN, they were not able to predict contamination potential. However, when they were used with other parameters, the predictive performance efficiency of the BPNN in terms of R, E, ME, RMSE, and pesticide occurrence "class" groups increased. Ancillary data include data collected during the study such as well depth and time of sample collection. The BPNN indicated that the ancillary data had more predictive power than the original data. The BPNN results will help researchers identify parameters to improve maps of aquifer sensitivity to pesticide contamination.

Riverbank filtration (RBF) is a low-cost water treatment technology in which surface water contaminants are removed or degraded as the infiltrating water moves from the river/lake to the pumping wells. The removal or degradation of contaminants is a combination of physicochemical and biological processes. This paper illustrates the development and application of three types of artificial neural networks (ANNs) to estimate the effectiveness of two RBF facilities in the US. The feed-forward back-propagation network (BPN) and radial basis function network (RBFN) model prediction results produced excellent agreement with measured data at a correlation coefficient above 0.99 for filtrate water quality parameters, including temperature as well as turbidity, heterotrophic bacteria, and coliform removal. In comparison, the fuzzy inference system network (FISN) predicted only temperature and bacteria removal with reasonable accuracy. It is shown that the predictive performances of the ANNs depend on the model structure and model inputs.

A dual-permeability model (S&#95;1D&#95;DUAL) was developed to simulate the transport of land-applied pesticides in macroporous media. In this model, one flow domain was represented by the bulk matrix and the other by the preferential flow domain (PFD) where water and chemicals move at faster rates. The model assumed the validity of Darcian flow and the advective-dispersive solute transport in each of the two domains with inter-domain transfer of water and solutes due to pressure and concentration gradients. It was conceptualized that sorption and biodegradation rates vary with soil depth as well as in each of the two flow domains. In addition to equilibrium sorption, kinetic sorption was simulated in the PFD. Simulations were conducted to evaluate the combined effects of preferential flow, depth- and domain-variant sorption, and degradation on leaching of two pesticides: one with strong sorption potential (trifluralin) and the other with weak sorption potential (atrazine). Simulation results for a test case showed that water flux in the PFD was three times more than in the matrix for selected storm events. When equilibrium sorption was considered, the simulated profile of trifluralin in each domain was similar; however, the atrazine profile was deeper in the PFD than in the bulk matrix under episodic storm events. With an assumption of negligible sorption in the PFD, both the atrazine and the trifluralin profiles moved twice deeper into the PFD. The simulated concentrations of the chemicals were several orders higher in the PFD than in the matrix, even at deeper depths. The volume fraction of the macropores and the sorption and biodegradation properties of the chemicals could also affect the amount of pesticides leaving the root zone. For an intense storm event, slow sorption reaction rates in the PFD produced higher breakthrough concentrations of atrazine at the bottom of the simulated soil profile, thus posing the risk for breakthrough of chemicals from the root zone.

Goal, Scope and Background: This glasshouse study is aimed at evaluating tropical plants for phytoremediation of petroleum hydrocarbon-contaminated saline sandy subsurface soils. Tropical plants were selected for their ability to tolerate high salinity and remove No. 2 diesel fuel in coastal topsoil prior to further investigation of the phytoremediation feasibility in deep contaminated soils. The residual petroleum-hydrocarbon contaminant at the John Rogers Tank Farm site, a former petroleum storage facility, at Hickam Air Force Base, Honolulu, Hawaii, is located in a coastal area. It lies below a layer of silt in the subsurface, in loamy sand characterized by moderate salinity and high pH. Little is known regarding the ability of tropical plants to remediate petroleum hydrocarbon-contaminated subsurface soil in Hawaiian and other Pacific Island ecosystems although suitable plants have been identified and utilized for bioremediation in surface soil or marine sediments., Methods: The experiments were conducted in long narrow pots under glasshouse conditions in two phases. A preliminary experiment was done with nine tropical plants: kiawe (Prosopis pallida), milo (Thespesia populnea), common ironwood (Casuarina equisetifolia), kou (Cordia subcordata), tropical coral tree (Erythrina variegata), false sandalwood (Myoporum sandwicense), beach naupaka (Scaevola sericea), oleander (Nerium oleander), and buffelgrass (Cenchrus ciliaris). These plants were screened for resistance to high salinity treatment (2% NaCl) and two diesel fuel levels (5 and 10 g No. 2 diesel fuel/kg soil) in separate treatments. Plants that showed good tolerance of both factors were further evaluated in a second phase for their efficacy in the phytoremediation of diesel-fuel petroleum hydrocarbons under moderate salinity treatment (1% NaCl)., Results: Tropical coral tree and buffelgrass were susceptible to either 2% NaCl or diesel fuel at 10 g/kg soil, but tolerant of diesel fuel at 5 g/kg soil. Kiawe, milo, kou, common ironwood, N. oleander, beach naupaka and false sandalwood were tolerant of high salinity (2% NaCl) or high diesel fuel level (10 g/kg soil). These seven plants were also tolerant of the combined adverse effects of a moderate salinity (1% NaCl) and 10 g diesel fuel/kg soil. Three trees, kiawe, milo and kou significantly accelerated the degradation of petroleum hydrocarbons in the soil spiked with 10 g diesel fuel/kg soil under a moderate salinity treatment (1% NaCl)., Conclusion: Thus the tropical woody plants, kiawe, milo and kou showed potential for use in phytoremediation of petroleum hydrocarbons in coastal tropical soils., Recommendations and Outlook: Two fast growing trees, milo and kou, appeared promising for further phytoremediation evaluation in experiments that simulate the soil profile at the field site.