The herbicides 2,4-diclorophenoxiacetic and 4-chloro-2-methylphenoxyacetic acids (2,4-D and MCPA) are widely used in agricultural practices worldwide. Not only are these practices responsible of surface waters contamination, but also agrochemical industries through the discharge of their liquid effluents. In this investigation, the ability of a 2,4-D degrading Delftia sp. strain to degrade the related compound MCPA and a mixture of both herbicides was assessed in batch reactors. The strain was also employed to remove and detoxify both herbicides from a synthetic effluent in a continuous reactor. Batch experiments were conducted in a 2-L aerobic microfermentor, at 28 °C. Continuous experiments were carried out in an aerobic downflow fixed-bed reactor. Bacterial growth was evaluated by the plate count method. Degradation of the compounds was evaluated by UV spectrophotometry, gas chromatography (GC), and chemical oxygen demand (COD). Toxicity was assessed before and after the continuous process by using Lactuca sativa seeds as test organisms. Delftia sp. was able to degrade 100 mg L⁻¹ of MCPA in 52 h. When the biodegradation assay was carried out with a mixture of 100 mg L⁻¹ of each herbicide, the process was accomplished in 56 h. In the continuous reactor, the strain showed high efficiency in the simultaneous removal of 100 mg L⁻¹ of each herbicide. Removals of 99.7, 99.5, and 95.0% were achieved for 2,4-D, MCPA, and COD, respectively. Samples from the influent of the continuous reactor showed high toxicity levels for Lactuca sativa seeds, while toxicity was not detected after the continuous process.

Stopped-flow technology and HPLC analysis were used to study the degradation mechanism and reaction kinetics of 4-chlorophenol (4-CP) in Fenton oxidation process. The results indicated that benzoquinone and hydroquinone were simultaneously produced in process of Fenton oxidizing 4-CP by stopped-flow technology analysis. The data obtained by HPLC showed that hydroquinone was generated in great quantities following the decrease of benzoquinone. It could be inferred by batch experiments that benzoquinone would be transformed into hydroquinone in Fenton process and hydroperoxyl radical (HO₂·) would take the main part in this process. In our study, there would exist two catalytic systems in Fenton process, and one was Fe²⁺and Fe³⁺, the other was hydroquinone and benzoquinone. Moreover, the rate constants of hydroquinone, benzoquinone, and 4-chlorocatechol were 2.78 × 10⁶ L s⁻¹ mol⁻¹, 9.38 × 10⁸ L s⁻¹ mol⁻¹, and 6.47 × 10⁶ L s⁻¹ mol⁻¹, respectively. Graphical Abstract

This study investigates the impact of future climate change on heavy metal (i.e., Cd and Zn) transport from soils to surface waters in a contaminated lowland catchment. The WALRUS hydrological model is employed in a semi-distributed manner to simulate current and future hydrological fluxes in the Dommel catchment in the Netherlands. The model is forced with climate change projections and the simulated fluxes are used as input to a metal transport model that simulates heavy metal concentrations and loads in quickflow and baseflow pathways. Metal transport is simulated under baseline climate (“2000–2010”) and future climate (“2090–2099”) conditions including scenarios for no climate change and climate change. The outcomes show an increase in Cd and Zn loads and the mean flux-weighted Cd and Zn concentrations in the discharged runoff, which is attributed to breakthrough of heavy metals from the soil system. Due to climate change, runoff enhances and leaching is accelerated, resulting in enhanced Cd and Zn loads. Mean flux-weighted concentrations in the discharged runoff increase during early summer and decrease during late summer and early autumn under the most extreme scenario of climate change. The results of this study provide improved understanding on the processes responsible for future changes in heavy metal contamination in lowland catchments.

Mercury (Hg) poses environmental and health risks due to its global distribution and high toxicity exhibited in some of its chemical forms. Although Hg is naturally present in the environment, human activities have increased its cycling among the land, atmosphere and ocean by a factor of three to five comparing the pre-industrial period to the present day. The Torviscosa chlor-alkali plant (CAP), which operated since the beginning of twentieth century, was one of the most important Cl₂ production capacity in the Northern Italy and was responsible for an uncontrolled discharge of Hg in the surrounding area. Previous studies reported the high degree of Hg pollution in soils, river sediments and surface waters of the area, but the Hg level in the atmospheric media was never taken into consideration. In this work, an integrated approach was applied with the aim to assess the level, distribution and dispersion of gaseous elemental mercury (GEM) close to the CAP area. GEM levels were monitored by means of four surveys conducted from September 2014 to July 2015, at fixed locations and covering an area of about 10 km² (including CAP area, Torviscosa village and reclaimed land), accomplished to Hg bioaccumulation measurements in selected lichens. The results indicate that the CAP area currently represents the main source of GEM in the Friuli Venezia Giulia region. The highest levels were found close to the old factory’s buildings (more than 5000 ng m⁻³), whereas other sites are less impacted. The emission of GEM is not clearly related to the intensity of solar radiation (temperature) at the soil level; however, this latter influences the release from the old buildings employed in the past for the production activities. The most important factor driving the GEM dispersion is the wind, as confirmed by the map of lichens bioaccumulation. In this context, the GEM plume partially affects the nearby village of Torviscosa (about 1 km), but the values found were always well below the international thresholds for residential areas, thus excluding the risk of inhalation for local inhabitants.

Biomass-derived biochar is considered as a promising heavy metal adsorbent, due to its favorable physicochemical properties, from aqueous solution as compared with other adsorbents. However, there is a limited number of studies on the effects of biochar produced from different feedstocks and pyrolytic temperatures on metal removal from metal-contaminated water. So in this study, the removal of the most prevalent heavy metals [(lead (Pb(II)), cadmium (Cd), and chromium (Cr)] by green waste biochar (GWB) and popular twigs biochar (PTB), produced at different pyrolytic temperatures, i.e., low 350 and high 650 °C, has been investigated, following the determination of physical and chemical properties of biochar. The efficiency of heavy metals removal of biochar was studied at different concentrations of heavy metals (10 and 100 μg mL⁻¹), biochar types and treatment duration (3, 6, 9, and 12 h) at isothermic condition of aqueous solution. Results revealed that both feedstock type and pyrolytic temperature to produce biochar significantly affected its metal sorption capacity. The maximum sorption capacities of all three metals, i.e., Pb (II), Cd, and Cr were determined in the GWB produced at low pyrolytic temperature 350 °C after 9 h of treatment duration at both high and low metal concentrations. This highest sorption capacity of all metals by low pyrolytic temperature produced GWB was due to its better physicochemical properties especially high surface area, cation exchange capacity, and oxygen-containing functional groups as compared with woody feedstock based high pyrolytic temperature produced PTB. Conclusively, low pyrolytic temperature produced GWB was evaluated as a potential adsorbent to efficiently reduced heavy metal concentration in metal-contaminated water.

Drought is a serious concern in many parts of the world, including in California, where paucity of available irrigation water has impaired crop production and soil health through salt accumulation. With extending water and salinity crises, there is a need for advanced salt and vegetation management. To develop more efficient management solutions, Slingram electromagnetic investigations and stochastic and statistical analyses were performed for determining optimal vegetable yields in a salt-affected farmland. The Slingram results were evaluated using multi-linear regression analyses, and the yield and salinity were characterized for central tendency, variance, distributions and symmetry. The yields of two studied vegetable crops, lettuce and tomato, increased with decreasing salinity load. The average lettuce and tomato yield potentials were 55 and 75%, respectively. The minimum yield potential for tomato was 9.5 times higher than that for lettuce. The mode value for conductivity (ECₑ) was 650 mS m⁻¹, which corresponded to 50% yield loss. The yield loss was <10% in locations with ECₑ < 250 mS m⁻¹. In zones with ECₑ > 850 mS m⁻¹, the yield reductions for lettuce and tomato reached up to 96 and 60%, respectively. About 57 and 82% of the field area could be limited to 20% yield potentials for tomato and lettuce, respectively. Lettuce had a higher cost benefit than tomato albeit with a greater yield potential of the latter crop. By delineating the spatial contours of salt-induced yield variability, vegetables can be grown in segmented soil zones based on salinity levels.

The soil saltiness in the Brazilian semiarid environment is a common problem caused by incorrect agricultural practices, allied to the local weather and soil condition. The use of phosphogypsum (PG) to recover these soils still is a concern since this material has in its composition natural radionuclides. An experiment was conducted to study the use of phosphogypsum to reduce the salinity and evaluate the bioavailability of radionuclides on the Brazilian semiarid region soils. The radionuclide content of phosphogypsum samples were previously analyzed by gamma spectrometry. Three differents doses of phosphogypsum were mixed with samples of surface soil in the greenhouse, and after a reaction time and irrigation, controlled soil samples + phosphogypsum underwent simple extractions based on the sequential extraction method by Tessier et al. Ra isotopes and ²¹⁰Pb in the extracted fractions were analyzed by counting alpha and beta. The higher concentration of Ra isotopes and ²¹⁰Pb were associated to residual fraction, followed by exchangeable fraction due to the low levels of carbonates, organic matter, and manganese and iron oxides. The use of phosphogypsum studied did not contribute to increase the ²²⁶Ra activity on the analyzed soils. ²²⁶Ra levels in phosphogypsum were lower than those recommended by the USEPA to allow the use of phosphogypsum in agricultural soils, but can contribute to the accumulation of ²²⁸Ra and ²¹⁰Pb. The phosphogypsum Imbituba promoted a satisfactory reduction of electrical conductivity in the soils, which indicates the possibility of recovery of these soils.

Advanced nitrogen (N)-removal onsite wastewater treatment systems (OWTS) are installed in coastal areas throughout the USA to reduce N loading to groundwater and marine waters. However, final effluent total nitrogen (TN) concentration from these systems is not always routinely monitored, making it difficult to determine the extent to which they contribute to N loads. We monitored the final effluent TN concentration of 42 advanced N-removal OWTS within the Greater Narragansett Bay Watershed, Rhode Island between March 2015 and August 2016. The compliance rate with the State of Rhode Island final effluent standard (TN ≤ 19 mg N/L) was 64.3, 70.6, and 75.0% for FAST, Advantex, and SeptiTech systems, respectively. The median (range) final effluent TN concentration (mg N/L) was 11.3 (0.1–41.6) for SeptiTech, 14.9 (0.6–61.6) for Advantex, and 17.1 (0.6–104.9) for FAST systems. Variation in final effluent TN concentration was not driven by temperature; TN concentrations plotted against effluent temperature values resulted in R ² values of 0.001 for FAST, 0.007 for Advantex, and 0.040 for SeptiTech systems. The median effluent TN concentration for all the systems in our study (16.7 mg N/L) was greater than reported for Barnstable County, MA systems (13.3 mg N/L), which are monitored quarterly. Depending on technology type, ammonium (NH₄⁺), nitrate (NO₃⁻), alkalinity, forward flow, biochemical oxygen demand (BOD), and effluent temperature best predicted effluent TN concentrations. Service providers made adjustments to seven underperforming systems, but TN was reduced to 19 mg N/L in only two of the seven systems. Advanced N-removal OWTS can reduce TN to meet regulations, and monitoring of these systems can enable service providers to proactively manage systems. However, improvement of performance may require recursive adjustments and long-term monitoring.

The Highveld and Waterberg regions in South Africa contain extensive coal fields and therefore have a high concentration of coal-fired power stations. Previous studies assessed the impact of atmospheric deposition of S- and N-containing species from anthropogenic sources in the region but did not include the effect of biogenic emissions. This study models biogenic NOX soil emissions for the regions and includes them in an atmospheric dispersion model to study the effects of biogenic emission on nitrogen deposition rates. Simulated sulfur deposition rates for the Highveld area are also reported on. Anthropogenic and biogenic sulfur and nitrogen emission sources were inventoried for the Highveld and Waterberg regions. Using previous work by Yienger and Levy, biogenic soil NOX emissions were quantified by constructing models for both areas using land use data, rainfall data, and atmospheric ground level temperatures from CALMET data. A CALPUFF dispersion model was used to predict deposition rates for S- and N-containing species with and without biogenic NOₓ emissions to determine the impact of biogenic emissions for the Highveld. As rainfall is highly variable in the region, meteorological data representative of high, average, and low rainfall years was used to determine the effect of rainfall on deposition rates for the various species. The biogenic NOₓ made up 3.96, 4.14, and 3.34% of total released NOₓ for 2001 (average rainfall), 2003 (low rainfall), and 2010 (high rainfall), respectively. Dry nitrogen deposition rates were affected most by the biogenic component, adding from 1.7 to 6.2% at various receptor locations. Wet deposition rates were affected very little (0.13 to 0.75%). Effect on total nitrogen deposition rates ranged from 0.32 to 1.77%. Biogenic emissions for the Waterberg area, being more arid, were calculated to be only 2.3% of total NOₓ emissions for the area and accordingly have little effect on deposition rates.

The potential application of commercial coffee as a source of electron donors for detoxifying hexavalent chromium [Cr(VI)]-contaminated water was investigated. Various amounts of coffee were reacted with 50 mg/L of artificially prepared Cr(VI)-contaminated water, and the Cr(VI) concentration was monitored as a function of the reaction time using the diphenylcarbazide colorimetric method with an Aquamate 8000 UV-Vis spectrophotometer at a 540-nm wavelength. When the ratio of the coffee mass applied to the volume of Cr(VI) solution was 75 g/L, more than 80% of the initial Cr(VI) disappeared within 5 min of reaction time, and the Cr(VI) concentration became lower than the detection limit of 1 mg/L within 20 min. More Cr(VI) disappeared as more coffee was introduced. In general, smaller particles of coffee were more effective at Cr(VI) reduction, but the advantage that particle size conferred disappeared once the coffee particle size was smaller than 125 μm. As a result, the reduction of the Cr(VI) in the solution was not considered to result from the surface catalytic reduction but by the electron transfer from the electron donors released from the applied coffee.