Land application of biochar has been increasingly recommended as a powerful strategy for carbon sequestration and soil remediation. However, the biochar particles, especially those in the nanoscale range, may migrate or carry the inherent contaminants along the soil profile, posing a potential risk to the groundwater. This study investigated the transport and retention of wood chip-derived biochar nanoparticles (NPs) in water-saturated columns packed with a paddy soil. The environmentally-relevant soil solution chemistry including ionic strength (0.10–50 mM), electrolyte type (NaCl and CaCl2), and natural organic matter (0–10 mg L−1 humic acid) were tested to elucidate their effects on the biochar NPs transport. Higher mobility of biochar NPs was observed in the soil at lower ionic strengths, with CaCl2 electrolyte being more effective than NaCl in decreasing biochar NPs transport. The retained biochar NPs in NaCl was re-entrained (∼57.7%) upon lowering transient pore-water ionic strength, indicating that biochar NPs were reversibly retained in the secondary minimum. In contrast, negligible re-entrainment of biochar NPs occurred in CaCl2 due to the primary minimum and/or particle aggregation. Humic acid increased the mobility of biochar NPs, likely due to enhanced electrosteric repulsive interactions. The transport behaviors of biochar NPs can be well interpreted by a two-site kinetic retention model that assumes reversible retention for one site, and irreversible retention for the other site. Our findings indicated that the transport of wood chip biochar NPs is significant in the paddy soil, highlighting the importance of understanding the mobility of biochar NPs in natural soils for accurately assessing their environmental impacts.

The effects of graphene oxide (GO) on the transport and deposition behaviors of colloids with different sizes in packed quartz sand were investigated in both NaCl (10 and 50 mM) and CaCl2 solutions (1 and 5 mM) at pH 6. Fluorescent carboxylate-modified polystyrene latex microspheres (CMLs) with size ranging from 0.2 to 2 μm were utilized as model colloids. Both breakthrough curves and retained profiles of colloids in the presence and absence of GO in suspensions under all examined solution conditions were analyzed. The breakthrough curves of all three different-sized CMLs with GO were higher yet the retained profiles were lower than those without GO at both examined ionic strengths in NaCl solutions. The observation showed that GO increased the transport and decreased the deposition of all three different-sized CMLs in NaCl solutions. However, in CaCl2 solutions, opposite observation was achieved at two different ionic strength conditions. Specifically, the presence of GO increased the transport and decreased the deposition of all three different-sized CMLs in 1 mM CaCl2 solutions, whereas, it decreased the transport and increased the deposition of all three different-sized CMLs in 5 mM CaCl2 solutions. Comparison the breakthrough curves and retained profiles of CMLs versus those of GO yielded that the overall transport and deposition behaviors of all three different-sized CMLs with GO copresent in suspensions agreed well with the transport and deposition behaviors of GO under all examined conditions. The transport and deposition behaviors of CMLs in packed porous media clearly were controlled by those of GO under the conditions investigated in present study due to the adsorption of CMLs onto GO surfaces. Our study showed that once released into natural environment, GO would adsorb (interact with) different types of colloids and thus have significant influence on the fate and transport of colloids in porous media.

Many antibiotics, including sulfonamides, are being frequently detected in soil and groundwater. Livestock waste is an important source of antibiotic pollution, and sulfonamides may be present along with organic-rich substances. This study aims to investigate the sorption reaction of two sulfonamides, sulfamethoxazole (SMZ) and sulfapyridine (SPY) in two organic-rich sorbents: a commercial peat soil (38.41% carbon content) and a composted manure (24.33% carbon content). Batch reactions were conducted to evaluate the impacts of pH (4.5–9.5) and background ions (0.001 M–0.1 M CaCl2) on their sorption. Both linear partitioning and Freundlich sorption isotherms fit the reaction well. The n values of Freundlich isotherm were close to 1 in most conditions suggesting that the hydrophobic partition is the major adsorption mechanism. In terms of SMZ, Kd declined with increases in the pH. SPY has a pyridine group that is responsible for adsorption at high pH values, and thus, no significant trend between Kd and pH was observed. At high pH ranges, SPY sorption deviated significantly from linear partitioning. The results suggested the sorption mechanism of these two sulfonamide antibiotics tended to be hydrophobic partitioning under most of the experimental conditions, especially at pH values lower than their corresponding pKa2. The fluorescence excitation emission matrix and dissolved organic carbon leaching test suggested composted manure has higher fulvic acid organics and that peat soil has higher humus-like organics. Small organic molecules showed stronger affinity toward sulfonamide antibiotics and cause the composted manure to exhibit higher sorption capacity. Overall, this study suggests that the chemical structure and properties of sulfonamides antibiotics and the type of organic matter in soils will greatly influence the fate and transport of these contaminants into the environment.

Simulating the storage of aerobic soils under water, the chemical speciation of heavy metals and arsenic was studied over a long-term reduction period. Time-dynamic and redox-discrete measurements in reactors were used to study geochemical changes. Large kinetic differences in the net-complexation quantities of heavy metals with sulfides was observed, and elevated pore water concentrations remained for a prolonged period (>1 year) specifically for As, B, Ba, Co, Mo, and Ni. Arsenic is associated to the iron phases as a co-precipitate or sorbed fraction to Fe-(hydr)oxides, and it is being released into solution as a consequence of the reduction of iron. The composition of dissolved organic matter (DOM) in reducing pore water was monitored, and relative contributions of fulvic, humic and hydrophylic compounds were measured via analytical batch procedures. Quantitative and qualitative shifts in organic compounds occur during reduction; DOM increased up to a factor 10, while fulvic acids become dominant over humic acids which disappear altogether as reduction progresses. Both the hydrophobic and hydrophilic fractions increase and may even become the dominant fraction.Reactive amorphous and crystalline iron phases, as well as dissolved FeII/FeIII speciation, were measured and used as input for the geochemical model to improve predictions for risk assessment to suboxic and anaerobic environments. The release of arsenic is related to readily reducible iron fractions that may be identified by 1 mM CaCl2 extraction procedure. Including DOM concentration shifts and compositional changes during reduction significantly improved model simulations, enabling the prediction of peak concentrations and identification of soils with increased emission risk. Practical methods are suggested to facilitate the practice of environmentally acceptable soil storage under water.

The use of road deicing salts in regions that experience cold winters is increasing the salinity of freshwater ecosystems, which threatens freshwater resources. Yet, the impacts of environmentally relevant road salt concentrations on freshwater organisms are not well understood, particularly in stream ecosystems where salinization is most severe. We tested the impacts of deicing salts—sodium chloride (NaCl), magnesium chloride (MgCl2), and calcium chloride (CaCl2)—on the growth and development of newly hatched rainbow trout (Oncorhynchus mykiss). We exposed rainbow trout to a wide range of environmentally relevant chloride concentrations (25, 230, 860, 1500, and 3000 mg Cl− L−1) over an ecologically relevant time period (25 d). We found that the deicing salts studied had distinct effects. MgCl2 did not affect rainbow trout growth at any concentration. NaCl had no effects at the lowest three concentrations, but rainbow trout length was reduced by 9% and mass by 27% at 3000 mg Cl− L−1. CaCl2 affected rainbow trout growth at 860 mg Cl− L−1 (5% reduced length; 16% reduced mass) and these effects became larger at higher concentrations (11% reduced length; 31% reduced mass). None of the deicing salts affected rainbow trout development. At sub-lethal and environmentally relevant concentrations, our results do not support the paradigm that MgCl2 is the most toxic deicing salt to fish, perhaps due to hydration effects on the Mg2+ cation. Our results do suggest different pathways for lethal and sub-lethal effects of road salts. Scaled to the population level, the reduced growth caused by NaCl and CaCl2 at critical early-life stages has the potential to negatively affect salmonid recruitment and population dynamics. Our findings have implications for environmental policy and management strategies that aim to reduce the impacts of salinization on freshwater organisms.

Although differential sensitivity of lichens to calcium excess has been documented previously at the community level, ecophysiological studies, which would shed light on the calcifuge or calcicole nature of lichens, are virtually absent. In the present study, we compared physiological responses of two morphologically similar foliose lichens, Dermatocarpon miniatum (calcicole lichen) and Umbilicaria hirsuta (calcifuge lichen) to Ca excess (up to 100 mM). The degree of total Ca uptake by the lichens after 24-h prolonged exposure was compared with selected physiological markers including levels of assimilation pigments, chlorophyll a fluorescence, soluble proteins, ergosterol, TBARS, and hydrogen peroxide. Both tested lichens accumulated Ca from the applied solutes of CaCl₂ by a dose-dependent manner, although excess of Ca did not change content of assimilation pigments in both tested lichens, as well as integrity of lichen symbiont membranes (tested as TBARS, K content, and ergosterol content) when compared to respective controls. However, we observed significant, concentration-dependent decrease of chlorophyll a fluorescence, content of soluble proteins, and hydrogen peroxide production in U. hirsuta, while in D. miniatum were all these parameters stable through all tested Ca concentrations.

The aim of this work was to analyse the response of Rosa rubiginosa to salinity induced by different concentrations of sodium chloride and calcium chloride (0, 25, 50, 100, 150 and 200 mM). Besides salt accumulation and pH changes, other parameters were investigated including photosynthetic activity, leaf water content, the dynamics of necrosis and chlorosis appearance and leaf drying. The study was complemented with microscopic analysis of changes in leaf anatomy. R. rubiginosa was more sensitive to the salinity induced by calcium chloride than by sodium chloride. Plant response to salinity differed depending of the salt concentration. These differences were manifested by higher dynamics of necrosis and chlorosis appearance and leaf drying. CaCl₂ showed greater inhibition of the photosynthetic apparatus and photosynthetic activity. Treatment with CaCl₂ caused more visible deformation of palisade cells, reduction in their density and overall reduction in leaf thickness. The study demonstrated higher accumulation of CaCl₂ in the soil, and thus greater limitations in water availability resulting in reduced leaf water content and quicker drying of leaves as compared with NaCl-treated plants.

Single extraction methods have been extensively used to assess the availability of metals in polluted soils. This work focused on checking the feasibility of several chemicals, i.e. CaCl₂, EDTA, diethylenetriaminepentaacetic acid (DTPA) and a low-molecular-weight organic acid mixture (rhizosphere-based method), to be used as extractants for mercury (Hg) in a soil from the Almadén mining district (Spain). Moreover, the effect of several experimental parameters, i.e. extraction time (0.5, 1, 2, 5, 16 and 24 h), concentration of extractant (0.01, 0.05, 0.1 and 1 M) and soil/extractant ratio (1:2, 1:5 and 1:10), on the amount of Hg extracted was investigated. The Hg extraction ability followed the descending order EDTA > rhizosphere-based method > DTPA ≈ CaCl₂. This ranking was attributed to the higher complexation power of EDTA and organic acids. It was also found that extraction times between 2 and 5 h are required to avoid underestimation of mobile Hg and re-adsorption of the Hg previously extracted. Although some exceptions were found, Hg extraction efficiency was generally enhanced with higher extractant concentrations. Finally, the amount of Hg extracted by the four extractants increased with decreasing soil/extractant ratios.

Regulatory limits on cadmium (Cd) content in food products are tending to become stricter, especially in cereals, which are a major contributor to dietary intake of Cd by humans. This is of particular importance for durum wheat, which accumulates more Cd than bread wheat. The contamination of durum wheat grain by Cd depends not only on the genotype but also to a large extent on soil Cd availability. Assessing the phytoavailability of Cd for durum wheat is thus crucial, and appropriate methods are required. For this purpose, we propose a statistical model to predict Cd accumulation in durum wheat grain based on soil geochemical properties related to Cd availability in French agricultural soils with low Cd contents and neutral to alkaline pH (soils commonly used to grow durum wheat). The best model is based on the concentration of total Cd in the soil solution, the pH of a soil CaCl₂ extract, the cation exchange capacity (CEC), and the content of manganese oxides (Tamm’s extraction) in the soil. The model variables suggest a major influence of cadmium buffering power of the soil and of Cd speciation in solution. The model successfully explains 88% of Cd variability in grains with, generally, below 0.02 mg Cd kg⁻¹ prediction error in wheat grain. Monte Carlo cross-validation indicated that model accuracy will suffice for the European Community project to reduce the regulatory limit from 0.2 to 0.15 mg Cd kg⁻¹ grain, but not for the intermediate step at 0.175 mg Cd kg⁻¹. The model will help farmers assess the risk that the Cd content of their durum wheat grain will exceed regulatory limits, and help food safety authorities test different regulatory thresholds to find a trade-off between food safety and the negative impact a too strict regulation could have on farmers.

The authors dealt with some hazardous elements, i.e. As, Cd, Co, Cr, Cu, Ni, Pb and Zn, contained in sands of the sandboxes localized in playgrounds of seven spas in southern Poland (CEE). The following determinations were made: the total contents of metals, the most mobile metals (water-leachable fraction) and the metals available to plants and organisms (CaCl₂- and EDTA-extractable fractions). The totals of the metals are below the upper limits of the values recommended for soils of the protected areas (type A). The mobility of the metals is low: the forms leachable with water range from 0.7% of the total content (TC) of Pb to 13.4% TC of Cd. The forms available to living organisms contain considerably higher quantities of the metals: from 2.3% TC of Ni to 22.6% TC of As in CaCl₂-extractable fractions and from 0.7% TC of Cr to 82% TC of As in EDTA-extractable fractions. An assessment of the health risk indicates that children are exposed to the metals present in the sandboxes mostly due to inadvertent swallowing of “dirt” from their hands. The highest are the HQᵢₙgₑₛₜᵢₒₙ indexes of As and Cr, both for the 3-year-old permanent spa residents (5.74E−02 and 1.71E−02, respectively) and the spa visitors of the same age (7.47E−03 and 2.22E−03, respectively) and the 6-year-old residents (4.31E−02 and 1.28E−02, respectively) and visitors (5.60E−03 and 1.66E−03, respectively). The health risk indexes HI in the case of non-cancerogenic substances for children 3 and 6 years old are for spa residents, 9.59E−02 and 7.19E−02, respectively, and for children visitors, who are exposed to environmental factors for a much shorter time than the residents, 1.25E−02 and 9.35E−03, respectively. All the risk indexes have their values significantly below 1, which proves the lack of deleterious effects resulting from the exposition of children to the elements considered. The children of both age groups, exposed to the cancerogenic substances, are endangered mainly by As. The risk values of the cancerogenic As for 3- and 6-year-old children residents are 1.27E−06 and 1.90E−06, respectively, and for children visitors of the same ages 1.65E−07 and 2.47E−07, respectively. These values are significantly lower than a permissible level of "1∙10E-05" and means that also in this case, the health risk is minimal. The risk values calculated for the remaining metals are much lower and follow the sequence Cr > Co > Cd. However, an adverse impact of some sand-contained pollutants that are attributed to the motor traffic (Cu, Zn, Ni, Cr, Co and Pb) and low emissions (mainly As and Cd) has been established in the spa resorts in question.