A 9-year water dataset from the Houston Ship Channel (HSC) was analyzed to understand partitioning in polychlorinated biphenyls (PCBs) and polychlorinated dibenzo-p-dioxins/polychlorinated dibenzofurans (PCDD/Fs). Total PCBs had more mass as dissolved (74 %) whereas total PCDD/Fs did not (11 %). Generally, the limited number of PCDD/Fs (only 2378 substituted) explained these differences though differences in chemical behavior beyond log K ₒw also likely influence partitioning. The particular fractionation seen in the HSC also seemed related to a wide variation in particulate organic carbon (POC)/dissolved organic carbon (DOC) ratio (0.42–180 %). Published and unaltered linear free energy and linear solvation energy relationships for DOC, POC, and particulate black carbon (BC) resulted in predictions that were at best 27 % (PCB) and 25 % root-mean-square error (RMSE) (PCDD/F) partition fraction compared to observed (using estimated BC/POC fractions of 10 and 25 %, respectively). These results show, at least in light of the uncertainties in this data (e.g., precise fraction of BC), that a 25 % accuracy in model prediction of operationally dissolved or suspended fraction for any one PCB or PCDD/F congener is the best prediction that may be expected. It is therefore recommended that site-specific data be used to calibrate most any water column-partitioning model if it is to be expected to describe what actually occurs in field conditions.

Zinc oxide (ZnO) nanoparticles were synthesized by precipitation and sol-gel methods. The aim of this study was to understand how different synthetic methods can affect the photocatalytic activity of ZnO nanoparticles. As-synthesized ZnO nanoparticles were characterized by X-ray diffraction (XRD) and UV-Visible spectroscopic techniques. XRD patterns of ZnO powders synthesized by precipitation and sol-gel methods revealed their hexagonal wurtzite structure with crystallite sizes of 30 and 28 nm, respectively. Their photocatalytic activities were evaluated by photocatalytic degradation of methylene blue, a common water pollutant, under UV radiation. The effects of operational parameters such as photocatalyst load and initial concentration of the dye on photocatalytic degradation of methylene blue were investigated. While the degradation of dye decreased over the studied dye concentration range of 20 to 100 mg/L, an optimum photocatalyst load of 250 mg/L was needed to achieve dye degradation as high as 81 and 92.5 % for ZnO prepared by precipitation and sol-gel methods, respectively. Assuming pseudo first-order reaction kinetics, this corresponded to rate constants of 8.4 × 10⁻³ and 12.4 × 10⁻³ min⁻¹, respectively. Hence, sol-gel method is preferred over precipitation method in order to achieve higher photocatalytic activity of ZnO nanostructures. Photocatalytic activity is further augmented by better choice of capping ligand for colloidal stabilization, starch being more effective than polyethylene glycol (PEG).

Cadmium (Cd) has known to produce many adverse effects on organs including placenta. Many essential transporters are involved in Cd transport pathways such as DMT-1, ZIP as well as L-VDCC. Fourteen pregnant women participated and were divided into two groups: high and low Cd-exposed (H-Cd, L-Cd) groups on the basis of their residential areas, Cd concentrations in the blood (B-Cd), urine (U-Cd), and placenta (P-Cd). The results showed that the B-Cd and U-Cd were significantly increased in H-Cd group (p < 0.05). Interestingly, the P-Cd in H-Cd group was elevated (p < 0.05) and positively related to their B-Cd and U-Cd values (p < 0.05). However, the mean cord blood Cd (C-Cd) concentration in H-Cd group was not significantly increased about 2.5-fold when comparing to L-Cd group. To determine the Cd accumulation in placental tissues, metallothionein-1A (MT-1A) and metallothionein-2A (MT-2A) expressions were used as biomarkers. The results revealed that mean MT-1A and MT-2A mRNAs and MT-1/2 proteins were up-regulated in H-Cd group (p < 0.05). In addition, the Ca channel alpha 1C (CACNA1C) mRNA and protein expressions were noticeably elevated in H-Cd group (p < 0.05). From these findings, we suggested that CACNA1C might be implicated in Cd transport in human placenta.

The aim of this study has been to measure the level of lead, cadmium, nitrates, and nitrites in the daily diets of children and adolescents from orphanages located in Krakow (Poland). Diets were collected over four seasons of 2009. The content of cadmium and lead was measured with flameless atomic absorption spectrometry. Nitrates and nitrites in diets were measured using the Griess colorimetric method. In all orphanages, the average intake of lead with daily diets, regardless of the season, ranged from 1.11 ± 0.15 to 22.59 ± 0.07 μg/kg bw/week. The average cadmium intake by children and adolescents ranged between 3.09 ± 0.21 and 20.36 ± 2.21 μg/kg bw/week and, for all orphanages, exceeded the tolerable weekly intake (TWI) level. Daily intake of nitrates and nitrites ranged respectively from 27 to 289 % and from 9 to 99 % of the acceptable daily intake (ADI). The youngest children, with lower body mass, were particularly sensitive to the excessive intakes of cadmium and nitrates.

Accurate modeling of soil water content is required for a reasonable prediction of crop yield and of agrochemical leaching in the field. However, complex mathematical models faced the difficult-to-calibrate parameters and the distinct knowledge between the developers and users. In this study, a deterministic model is presented and is used to investigate the effects of controlled drainage on soil moisture dynamics in a shallow groundwater area. This simplified one-dimensional model is formulated to simulate soil moisture in the field on a daily basis and takes into account only the vertical hydrological processes. A linear assumption is proposed and is used to calculate the capillary rise from the groundwater. The pipe drainage volume is calculated by using a steady-state approximation method and the leakage rate is calculated as a function of soil moisture. The model is successfully calibrated by using field experiment data from four different pipe drainage treatments with several field observations. The model was validated by comparing the simulations with observed soil water content during the experimental seasons. The comparison results demonstrated the robustness and effectiveness of the model in the prediction of average soil moisture values. The input data required to run the model are widely available and can be measured easily in the field. It is observed that controlled drainage results in lower groundwater contribution to the root zone and lower depth of percolation to the groundwater, thus helping in the maintenance of a low level of soil salinity in the root zone.

Glyphosate is a worldwide-used herbicide occurring in many monitoring campaigns. Efficient technologies are currently unavailable for glyphosate removal from waters. In this work, a SBA-15 mesoporous silica-based material (Fe-NH₂-SBA-15) was synthesized and studied for the adsorption of glyphosate from waters. In order to promote specific interactions between the sorbent and glyphosate via phosphoric group, iron oxide nanoparticles were encapsulated and a surface functionalization with (3-aminopropyl)triethoxysilane was accomplished. The adsorption of glyphosate on Fe-NH₂-SBA-15 was investigated as a function of (i) pH, (ii) ionic strength (I), and (iii) adsorbate to adsorbent ratio (C), using a two-level, three-factor experimental design. The experimental design allowed for understanding the effect of the abovementioned variables and for proposing experimental conditions for quantitative removal (pH = 2.1, I = 1⋅10⁻² M and C = 0.35) under both batch and dynamic conditions. Interaction mechanism between glyphosate and Fe-NH₂-SBA-15 sorbent was elucidated by studying the adsorption behavior of sorbents derived from the intermediate stages of synthesis and by desorption tests. Fe-NH₂-SBA-15 sorbent can be quantitatively regenerated by 12.5 mM NaOH, and can be reused at least for five adsorption/desorption cycles. Quantitative removal of glyphosate from inlet and effluent wastewaters from a wastewater treatment plant is shown.

For the purpose of investigating the effect of landfill leachate on the characteristics of organic matter in groundwater, groundwater samples were collected near and in a landfill site, and dissolved organic matter (DOM) was extracted from the groundwater samples and characterized by excitation–emission matrix (EEM) fluorescence spectra combined with fluorescence regional integration (FRI) and self-organizing map (SOM). The results showed that the groundwater DOM comprised humic-, fulvic-, and protein-like substances. The concentration of humic-like matter showed no obvious variation for all groundwater except the sample collected in the landfill site. Fulvic-like substance content decreased when the groundwater was polluted by landfill leachates. There were two kinds of protein-like matter in the groundwater. One kind was bound to humic-like substances, and its content did not change along with groundwater pollution. However, the other kind was present as “free” molecules or else bound in proteins, and its concentration increased significantly when the groundwater was polluted by landfill leachates. The FRI and SOM methods both can characterize the composition and evolution of DOM in the groundwater. However, the SOM analysis can identify whether protein-like moieties was bound to humic-like matter.

Whereas the response of lotic benthic macroinvertebrates to different environmental stressors is a widespread practice nowadays in assessing the water and habitat quality, the use of hyporheic zone invertebrates is still in its infancy. In this study, classification and regression trees analysis were employed in order to assess the ecological requirements and the potential as bioindicators for the hyporheic zone invertebrates inhabiting four lowland chalk rivers (south England) with contrasting eutrophication levels (based on surface nitrate concentrations) and magnitude of land use (based on percentage of fine sediments load and median interstitial space). Samples of fauna, water and sediment were sampled twice, during low (summer) and high (winter) groundwater level, at depths of 20 and 35 cm. Certain groups of invertebrates (Glossosomatidae and Psychomyiidae caddisflies, and riffle beetles) proved to be good indicators of rural catchments, moderately eutrophic and with high fine sediment load. A diverse community dominated by microcrustaceans (copepods and ostracods) were found as good indicators of highly eutrophic urban streams, with moderate-high fine sediment load. However, the use of other taxonomic groups (e.g. chironomids, oligochaetes, nematodes, water mites and the amphipod Gammarus pulex), very widespread in the hyporheic zone of all sampled rivers, is of limited use because of their high tolerance to the analysed stressors. We recommend the use of certain taxonomic groups (comprising both meiofauna and macroinvertebrates) dwelling in the chalk hyporheic zone as indicators of eutrophication and colmation and, along with routine benthic sampling protocols, for a more comprehensive water and habitat quality assessment of chalk rivers.

Experimental findings of sonophotocatalytic process were used in degradation of hydroquinone to assess kinetic modeling and determine the effect of various active radical species. First, the effects of three photocatalytic, sonocatalytic, and sonophotocatalytic processes were studied for hydroquinone removal to determine kinetic constants and calculate the activation energy of reactions, and then the selected process was evaluated to determine active radical species. The reactor was composed of two parts, one included ultrasonic probe (sonocatalytic part) with powers 22, 80, and 176 W and the second part was the location of UV lamp (photocatalytic part) with tubular flow and power 15 W. After three systems were examined and the efficient system was selected, the role of different active species such as hydroxyl radical (OH·), superoxide radical (O₂ ·⁻), hole (h⁺), electrons (e ⁻), and single oxygen molecule (¹O₂) and contribution of each of them were determined in hydroquinone degradation. According to tests, the results of this study showed that sonophotocatalytic integrated method as selected system among three systems studied followed the first-order equation for hydroquinone degradation and active hydroxyl species with 45 % and electron and hole with 15 and 10 %, respectively, had the highest and lowest contributions to conversion of hydroquinone. The findings showed that dissolved oxygen increases the capability of active radical formation so that 28.2 % of hydroquinone removal was increased under aeration compared to without aeration. Also, removal efficiency decreased 62 % with N₂ injection due to the withdrawal of oxygen from the sample. By adding 25 Mm of sodium azide (NaN₃) to stock solution, 46.5 % reduction was developed because single oxygen (¹O₂) played the role of an active species. The advantages of integrated sonocatalytic and photocatalytic method are the generation of active radical species with more variety and ultimately the formation of higher amounts of powerful hydroxyl radical that increases degradation rates of refractory compounds and low-risk internal and final products. It has an appropriate performance in the degradation of refractory compounds by optimizing effective operational factors.

In this study, we investigated the impact of potential emission sources and transport pathways on annual and seasonal PM₁₀ loadings in an urban area of Belgrade (Serbia). The analyzed dataset comprised PM₁₀ mass concentrations for the period 2003–2015, as well as their chemical composition (organic/elemental carbon, benzo[a]pyrene, As, Cd, Cr, Mn, Ni, Pb, Cl⁻, Na⁺, Mg²⁺, Ca²⁺, K⁺, NO₃⁻, SO₄²⁻, and NH₄⁺), meteorological parameters, and concentrations of inorganic gaseous pollutants and soot for the period 2011–2015. The combination of different methods, such as source apportionment (Unmix), ensemble learning method (random forest), and multifractal and inverse multifractal analysis, was utilized in order to obtain a detailed description of the PM₁₀ origin and spatio-temporal distribution and to determine their relationship with other pollutants and meteorological parameters. The contribution of long-range and regional transport was estimated by means of trajectory sector analysis, whereas the hybrid receptor models were applied to identify potential areas of concern.