Comparison of Phytoscreening and Direct‐Push‐Based Site Investigation at a Rural Megasite Contaminated with Chlorinated Ethenes

The reliable characterization of subsurface contamination of spatially extended contaminated sites is a challenging task, especially with an unknown history of land use. Conventional technologies often fail due to temporal and financial constraints and thus hinder the redevelopment of abandoned areas in particular. Here we compare two site screening techniques that can be applied quickly at relatively low cost, namely Direct Push (DP)‐based groundwater sampling and tree core sampling. The effectiveness of both methods is compared for a rural megasite contaminated with chlorinated hydrocarbons. Unexpected pollution hot spots could be identified using both of these methods, while tree coring even enabled the delineation of the contaminant plume flowing into an adjacent wetland inaccessible for DP units. Both methods showed a good agreement in revealing the spatial pattern of the contamination. The correlation between groundwater concentrations and equivalent concentrations in wood was linear and highly significant for trichloroethene. Correlation was less obvious for its metabolite cis‐dichloroethene, but still significant. As outcome of our study we recommend tree coring and for initial screening in combination with a DP sampling to retrieve quantitative data on groundwater pollutants in order to assess the contamination situation of a non‐ or only partly investigated site. The subsequent placement of monitoring wells for long‐term monitoring of contamination levels is recommended. A combination of methods would achieve more relevant information at comparable or possibly even lower efforts in comparison to a conventional site investigation.     

Simultaneous Analysis of Natural Free Estrogens and Their Conjugates in Wastewater by GC‐MS

A solid‐phase extraction (SPE)‐gas chromatography (GC)‐mass spectrometry (MS) analytical method was developed for the simultaneous analysis of natural free estrogens and their conjugates in wastewater samples. Natural free estrogens and their conjugates in wastewater were successfully separated by the oasis hydrophilic‐lipophilic balance solid phase extraction (Oasis HLB SPE) method, and the conjugates were initially enzyme hydrolyzed by β‐glucuronidase or arylsulfatase from Helix pomatia prior to derivatization. N‐methyl‐N‐(tert‐butyldimethylsilyl)trifluoroacetamide (MTBSTFA) plus 1% tert‐butyldimetheylchlorosilane (TBDMCS) was chosen as the derivatization reagent, and the most appropriate conditions of derivatization were determined to be at 95°C for 90 min. The recovery ratios of nine target chemicals were determined by spiking them in 1 L of ultra‐purified water or the influent of a wastewater treatment plant (WWTP). The recovery ratios of six out of nine for the analytes ranged from 73.3–114.9% with relative standard deviations (RSD) from 1.6–19.9%. The established method was successfully applied to environmental wastewater samples which were collected from one municipal wastewater treatment plant (WWTP) in Osaka, Japan, for the determination of natural free estrogens and their conjugates. In the influent sample, E1, E2, E1‐3S, E3‐3S, and E1‐3G were detected at concentrations of 16.6, 9.6, 8.2, 21.9, and 3.2 ng L^–1, respectively. However, only E1 was detected at a high concentration of 44 ng L^–1 in the effluent sample, suggesting that it is the dominant natural free estrogen in the effluent.     

Solid‐Phase Removal of Dissolved Organic Species from Water and Identification by GC–MS

A method is described for the detection and identification of dissolved organic compounds (DOCs) in various water samples. Acid treated active silica gel sorbent (pH 3) was packed into a micro‐column and used as a solid‐phase extraction medium for adsorption of DOCs. Silica particles‐adsorbed‐organic species were then divided into equal portions followed by suspension into various organic solvents of different polarities such as methanol, acetone, ethyl acetate, and toluene. Suspended silica‐adsorbed‐organic species were shaken for 1 h at room temperature and the organic extracts were subjected to GC–MS analysis under temperature programming conditions for qualitative detection and identification of these species. Blank solvents and silica samples were also subjected to the same extraction procedures and GC–MS analysis for comparison. The mass spectrum of each eluted chromatographic peak was library searched or manually interpreted to identify the compound.     

Problems and Solutions in Pesticide Analysis Using Solid‐phase Extraction (SPE) and Gas Chromatography Ion‐trap Mass Spectrometry Detection (GC‐MS)

In the present study an analytical method was tested for the determination of selected pesticides and metabolites using solid‐phase extraction (SPE) and gas chromatography ion‐trap mass spectrometry (GC‐MS). The extraction efficiency of C18, Isolut ENV+, and Lichrolut EN for SPE was compared for trifluralin, fenitrothion, endosulfan, propargite, 2,4‐D, 3‐methyl‐4‐nitrophenol, 2‐(4‐tert‐butylphenoxy)cyclohexanol, endosulfan sulfate, and 2,4‐dichlorophenol. Isolut ENV+ and C18 showed good results as sorbents and acetone as an elution solvent for SPE for the selected pesticides. Recoveries varied between 36% and 176% with a relative standard deviation of 2...18%. Because of coextracts from the SPE materials, recovery values higher than 100% were obtained for fenitrothion, endosulfan sulfate, and 2,4‐D with C18 as well as for endosulfan sulfate and 3‐methyl‐4‐nitrophenol with Isolut ENV+. A standard addition method was used to verify the occurrence of coextracts in the sample after SPE.     

Temperature‐Activated Auto‐Decomposition Reactions: An Under‐Utilized In Situ Remediation Solution

The remediation industry has witnessed multiple innovations arising from a greater understanding of the physical, chemical, and biological processes that control the fate and transport of chemicals in the subsurface environment. In addition, increasing emphasis is being placed on remediation solutions that are greener, simpler, and more resource efficient. The positive impacts that can be derived from this emphasis include reduced energy consumption, reduced waste emissions, and lower costs. Temperature‐activated auto‐decomposition reactions represent a potentially underutilized option for the in situ remediation of certain organic contaminants, and an option that can be both highly effective and greener than other available technologies.     

A Comparison of Data‐Driven Groundwater Vulnerability Assessment Methods

Increasing availability of geo‐environmental data has promoted the use of statistical methods to assess groundwater vulnerability. Nitrate is a widespread anthropogenic contaminant in groundwater and its occurrence can be used to identify aquifer settings vulnerable to contamination. In this study, multivariate Weights of Evidence (WofE) and Logistic Regression (LR) methods, where the response variable is binary, were used to evaluate the role and importance of a number of explanatory variables associated with nitrate sources and occurrence in groundwater in the Milan District (central part of the Po Plain, Italy). The results of these models have been used to map the spatial variation of groundwater vulnerability to nitrate in the region, and we compare the similarities and differences of their spatial patterns and associated explanatory variables. We modify the standard WofE method used in previous groundwater vulnerability studies to a form analogous to that used in LR; this provides a framework to compare the results of both models and reduces the effect of sampling bias on the results of the standard WofE model. In addition, a nonlinear Generalized Additive Model has been used to extend the LR analysis. Both approaches improved discrimination of the standard WofE and LR models, as measured by the c‐statistic. Groundwater vulnerability probability outputs, based on rank‐order classification of the respective model results, were similar in spatial patterns and identified similar strong explanatory variables associated with nitrate source (population density as a proxy for sewage systems and septic sources) and nitrate occurrence (groundwater depth).     

Fate of Benzalkonium Chloride in a Sewage Sludge Low Temperature Conversion Process Investigated by LC‐LC/ESI‐MS/MS

Thermocatalytic low temperature conversion (LTC) is a new method for the disposal of sewage sludge. Using this method, sludge is converted into a residual solid (coal) along with reaction water, oil, and non‐condensable gases. The oil can be used as an energy source and the coal as a substitute for charcoal. To this end, it is important to determine whether there are any easily available contaminants present in the coal generated by the process. Contaminants that can be strongly sorbed by sewage sludge solids are, e. g., pharmaceuticals and disinfectants. As an example the fate of the persistent and strong adsorbing disinfectant benzalkonium chloride (BAC) has been investigated within the LTC process. The sewage sludge was spiked with BAC and then subjected to the LTC process. The resulting coal was extracted and analyzed using LC‐LC/ESI‐MS/MS (ion trap). BAC could not be detected in the LTC coal, although it could be extracted from the spiked sludge before the LTC treatment. It can thus be concluded that the investigated compound is not easily available in the coal, and hence that its use does not present a risk.     

Photodegradation,Photocatalytic, and Aerobic Biodegradation of Sulfisomidine and Identification of Transformation Products by LC–UV‐MS/MS

Much attention has recently been devoted to the fate and effects of pharmaceuticals in the water cycle. Removal of antibiotics in effluents by photo‐treatment or biodegradation is a topic currently under discussion. Degradation and removal efficiencies of sulfisomidine (SUI) by photodegradation and aerobic biodegradability were studied. SUI behavior was monitored during photolysis and photocatalysis (catalyst titanium dioxide) using 150‐W medium‐pressure Hg lamp. Also an aerobic bacterial degradation test from the OECD series (closed bottle test (CBT, OECD 301 D)) was performed. The primary elimination of SUI was monitored. Structures of photo‐degradation products were assessed by chromatographic separation on a C18 column with ultraviolet detection at 270 nm and ion trap MS. The results demonstrate that SUI is not readily biodegradable in CBT. Photo catalysis was more is effective than photolysis. SUI underwent photodegradation and several SUI photoproducts were identified. Accordingly, the photodegradation pathway of SUI was postulated. When reaching the aquatic environment, SUI and its photo products can constitute a risk to the environment.     

A Low‐Cost,In Situ Resistivity and Temperature Monitoring System

We present a low‐cost, reliable method for long‐term in situ autonomous monitoring of subsurface resistivity and temperature in a shallow, moderately heterogeneous subsurface. Probes, to be left in situ, were constructed at relatively low cost with an electrode spacing of 5 cm. Once installed, these were wired to the CR‐1000 Campbell Scientific Inc. datalogger at the surface to electrically image infiltration fronts in the shallow subsurface. This system was constructed and installed in June 2005 to collect apparent resistivity and temperature data from 96 subsurface electrodes set to a pole‐pole resistivity array pattern and 14 thermistors at regular intervals of 30 cm through May of 2008. From these data, a temperature and resistivity relationship was determined within the vadose zone (to a depth of ~1 m) and within the saturated zone (at depths between 1 and 2 m). The high vertical resolution of the data with resistivity measurements on a scale of 5‐cm spacing coupled with surface precipitation measurements taken at 3‐min intervals for a period of roughly 3 years allowed unique observations of infiltration related to seasonal changes. Both the vertical resistivity instrument probes and the data logger system functioned well for the duration of the test period and demonstrated the capability of this low‐cost monitoring system.     

Adsorption Kinetic Modeling of Safranin onto Rice Husk Biomatrix Using Pseudo‐first‐ and Pseudo‐second‐order Kinetic Models: Comparison of Linear and Non‐linear Methods

Batch kinetic studies were carried out for the removal of safranin from aqueous solution using a biomatrix prepared from rice husk. The adsorption kinetic data were modeled using the pseudo‐first‐order and pseudo‐second‐order kinetic equations. The linear and non‐linear forms of these two widely used kinetic models were compared in this study. In order to determine the best‐fitting equation, the coefficient of determination (r²), the sum of the squares of the errors (SSE), sum of the absolute errors (SAE), average relative error (ARE), hybrid fractional error function (HYBRID), Marquardt's percent standard deviation (MPSD), and the Chi‐squared test (χ²) were used as error analysis methods. Results showed that the non‐linear forms of pseudo‐first‐order and pseudo‐second‐order models were more suitable than the linear forms for fitting the experimental data. Non‐linear method is thus more appropriate for estimating the kinetic parameters and should primarily be used to describe adsorption kinetics.     

A Comparison of Hyporheic Transport at a Cross‐Vane Structure and Natural Riffle

While restoring hyporheic flowpaths has been cited as a benefit to stream restoration structures, little documentation exists confirming that constructed restoration structures induce comparable hyporheic exchange to natural stream features. This study compares a stream restoration structure (cross‐vane) to a natural feature (riffle) concurrently in the same stream reach using time‐lapsed electrical resistivity (ER) tomography. Using this hydrogeophysical approach, we were able to quantify hyporheic extent and transport beneath the cross‐vane structure and the riffle. We interpret from the geophysical data that the cross‐vane and the natural riffle induced spatially and temporally unique hyporheic extent and transport, and the cross‐vane created both spatially larger and temporally longer hyporheic flowpaths than the natural riffle. Tracer from the 4.67‐h injection was detected along flowpaths for 4.6 h at the cross‐vane and 4.2 h at the riffle. The spatial extent of the hyporheic zone at the cross‐vane was 12% larger than that at the riffle. We compare ER results of this study to vertical fluxes calculated from temperature profiles and conclude significant differences in the interpretation of hyporheic transport from these different field techniques. Results of this study demonstrate a high degree of heterogeneity in transport metrics at both the cross‐vane and the riffle and differences between the hyporheic flowpath networks at the two different features. Our results suggest that restoration structures may be capable of creating sufficient exchange flux and timescales of transport to achieve the same ecological functions as natural features, but engineering of the physical and biogeochemical environment may be necessary to realize these benefits.     

Comparison of P‐wave attenuation models of wave‐induced flow

Wave‐induced oscillatory fluid flow in the vicinity of inclusions embedded in porous rocks is one of the main causes for P‐wave dispersion and attenuation at seismic frequencies. Hence, the P‐wave velocity depends on wave frequency, porosity, saturation, and other rock parameters. Several analytical models quantify this wave‐induced flow attenuation and result in characteristic velocity–saturation relations. Here, we compare some of these models by analyzing their low‐ and high‐frequency asymptotic behaviours and by applying them to measured velocity–saturation relations. Specifically, the Biot–Rayleigh model considering spherical inclusions embedded in an isotropic rock matrix is compared with White's and Johnson's models of patchy saturation. The modeling of laboratory data for tight sandstone and limestone indicates that, by selecting appropriate inclusion size, the Biot‐Rayleigh predictions are close to the measured values, particularly for intermediate and high water saturations.     

Comparison of nutrient loss pathways: Run‐off and seepage flow in Vertisols

Recent studies have highlighted the agronomic and environmental importance of phosphorus (P) movement through the soil profile. Thus, faced with challenges such as high‐profile cases of P enrichment of surface water, better understanding of nutrient movement through soil is needed to better manage agricultural fertilizers and manures and their contribution to water quality degradation. In particular, field‐scale research is especially needed in soils with preferential flow transport pathways. Thus, we collected nitrogen (N) and P transport data in run‐off and seepage (lateral subsurface return flow) from 13 field‐ and farm‐scale watersheds on Vertisols in Central Texas for a 14‐year period. For 2004–2017, seepage accounted for ~20% of the total surface flow, and nutrient concentrations were generally similar in run‐off and seepage. As surface run‐off contributed ~80% of the flow, it follows that median annual N and P loads in run‐off were significantly greater than in seepage for every watershed. N loads in both run‐off and seepage flow from cultivated land were an order of magnitude greater than in native prairie and improved pasture, and the highest run‐off and seepage P loads both occurred on cultivated land with organic fertilizer sources. Increasing watershed scale (size) did not to produce consistent patterns in N or P loss in run‐off or seepage. Land use and watershed scale produced significant differences in seepage volume but did not affect run‐off volumes or total surface flow/rainfall. Although less significant in terms of total offsite flux, nutrient movement in vadose zones has important agronomic and environmental implications as considerable N and P are transported through and within the root zone and eventually offsite. And in terms of P, this contradicts the traditionally held scientific viewpoint that P movement through the vadose zone is unimportant agronomically and environmentally.     

A Mini‐Review of E‐Waste Management in Brazil: Perspectives and Challenges

The accelerated production and replacement of new electrical and electronic equipment demonstrates a tendency for the proportional increase in the generation of e‐waste. Developing countries experience similar social and environmental consequences from this trend, which compounds the other challenges associated with the already poor solid waste management in these regions. Moreover, the dangerous composition of some e‐waste amplifies the problems related to managing these materials. This mini‐review presents a brief overview of e‐waste management in Brazil, including technical aspects, scientific studies, and the challenges ahead. With the Brazilian National Policy of Solid Waste already in place, technical and scientific studies endorse measures that range from incorporating the informal recycling sector into the e‐waste management sector to encouraging the expansion of the recycling industry. All such actions, combined with an intensified commitment of electronic equipment manufacturers to reverse logistics, can improve e‐waste management in Brazil.     

Comparison of fractional bed‐material load ­computation methods in sand‐bed channels

This paper presents a comparison of different fractional bed‐material load computation methods in sand‐bed channels. These methods include the direct computation by size fraction approach of Einstein, Laursen and Toffaleti; the bed material fraction (BMF) approach using equations of Engelund and Hansen, Ackers and White, Yang, and Karim's modified BMF method; and the transport capacity fraction (TCF) approach using the transport capacity distribution functions of Karim and Kennedy, Li, and Wu and Molinas. Over 150 sets of flume and field data in the sand size range containing a total of 1007 data points are used to evaluate and compare the accuracy of these methods. Statistical analysis and graphical comparison are utilized to demonstrate the performance and variations in different methods. Overall, the Einstein method underpredicts the transport rate for finer sizes and overpredicts for the coarser sizes, while the other methods overestimate the finer fractions and underestimate the coarser fractions. The Wu and Molinas method, which was developed to account for these deficiencies, is shown to significantly improve fractional bed‐material load computations. The Karim and Kennedy method is also found to be applicable. Copyright © 2000 John Wiley & Sons, Ltd.     

In Situ Bioremediation of Toluene‐Polluted Vadose Zone: Integrated Column and Wetland Study

A vertical soil column setup integrated with wetlands is developed to study the biodegradation and transport of toluene, a light non‐aqueous phase liquid (LNAPL), in the subsurface environment. LNAPL‐contaminated water is applied to infiltrate from the top of the soil column. The observed and simulated breakthrough curves show high equilibrium concentration at top ports rather than at lower ports, indicating effective toluene biodegradation with soil depth. The observed equilibrium concentration of toluene is higher in the case of unplanted wetland, asserting an accelerated biodegradation rate in the planted case. A difference in the relative concentration of toluene between input and output fluxes at 100 h is found as 13.34% and 30.86% for planted and unplanted wetland setups, respectively. Estimated biodegradation rates show that toluene degradation is 2.5 times faster in the planted wetland setup. In addition, the difference in the observed bacterial count and dissolved oxygen prove that toluene degraded aerobically at a faster rate in the planted setup. Simulations show that as time reached 80–100 h, there is no significant change in concentration profile, thereby confirming the equilibrium condition. The results of this study will be useful to frame plant‐assisted bioremediation techniques for LNAPL‐contaminated soil–water resources in the field.