Management and destruction of obsolete pesticides and the remediation of pesticide-contaminated soil are significant global issues with importance in agriculture, environmental health and quality of life. Pesticide use and management have a history of problems because of insufficient knowledge of proper planning, storage, and use. This manuscript reviews recent literature with an emphasis on the management of obsolete pesticides and remediation of pesticide-contaminated soil. The rhizosphere of plants is a zone of active remediation. Plants also take up contaminated water and remove pesticides from soil. The beneficial effects of growing plants in pesticide-contaminated soil include pesticide transformation by both plant and microbial enzymes. This review addresses recent advances in the remediation of pesticide-contaminated soil with an emphasis on processes that are simple and can be applied widely in any country.

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HIGHLIGHTS • Manganese and arsenic concentrations are elevated in Murshidabad groundwater. • Manganese release appears to be independent of dissolved organic matter quality. • Mineral precipitation and dissolution reactions impact fate of manganese. • Arsenic concentrations are related to dissolved organic matter quantity and quality. The prevalence of manganese (Mn) in Southeast Asian drinking water has recently become a topic of discussion, particularly when concurrent with elevated arsenic (As). Although Mn groundwater geochemistry has been studied, the link between dissolved organic matter (DOM) quality and Mn release is less understood. This work evaluates characteristics of DOM, redox chemistry, and the distribution of Mn within Murshidabad, West Bengal, India. Shallow aquifer samples were analyzed for cations, anions, dissolved organic carbon, and DOM properties using 3-dimensional fluorescence excitation emission matrices followed by parallel factor modeling analyses. Two biogeochemical regimes are apparent, separated geographically by the river Bhagirathi. East of the river, where E h and nitrate (NO − 3) values are low, humic-like DOM coexists with high dissolved Mn, As, and Fe. West of the river, lower dissolved As and Fe concentrations are coupled with more protein-like DOM and higher NO − 3 and E h values. Dissolved Mn concentrations are elevated in both regions. Based on the distribution of available electron acceptors, it is hypothesized that groundwater east of the Bhagirathi, which is more reducing and enriched in dissolved Fe and Mn but depleted in NO − 3 , is chemically dominated by Mn(IV)/Fe(III) reduction processes. West of the river where NO − 3 is abundant yet dissolved Fe is absent, NO − 3 and Mn(IV) likely buffer redox conditions such that E h values are not sufficiently reducing to release Fe into the dissolved phase. The co-occurrence of humic-like Vega et al. Biogeochemical Controls of Mn and As in Shallow Aquifers DOM with dissolved As, Fe, and Mn in the more reducing aquifers may reflect complex formation between humic DOM and metals, as well as electron shuttling processes involving humic DOM, which may enhance metal(loid) release. Saturation indices of rhodochrosite (MnCO 3) suggest that precipitation is thermodynamically favorable in a greater proportion of the more reducing sites, however humic DOM-Mn complexes may be inhibiting MnCO 3 precipitation. Where dissolved arsenic concentrations are low, it is postulated that Mn(IV) reduction is oxidizing As(III) to As(V), increasing the potential for re-adsorption of As(V) onto relatively stable, un-reduced or newly precipitated Fe-oxides. Manganese release appears to be independent of DOM quality, as it persists in both humic and protein-like DOM environments.

Constructed wetland treatment systems are used to remove selenium (Se) from flue-gas desulfurization (FGD) wastewater (WW). However, direct confirmation of the mechanism responsible for FGD WW Se retention in soil is lacking. A laboratory-based soil column study was performed to develop an evidence-based mechanism of Se retention and to study the behavior and the retention capacity of FGD WW constituents in water-saturated soil. A deoxygenated 1:1 mixture of FGD WW and raw water was delivered to the columns bottom-up at a flux of 1.68 cm d for 100 d. Some of the columns were flushed with the raw water at the same rate for an additional 100 d. Column effluent was analyzed for constituents of concern. Results showed a complete retention of FGD WW Se in the soil materials. Boron and fluorine were partially retained; however, sulfur, sodium, and chlorine retention was poor, agreeing with field observations. The FGD WW Se was retained in soil near the inlet end of the columns, indicating its limited mobility under reduced conditions. Sequential extraction procedure revealed that retained Se was mainly sequestered as stable/residual forms. Bulk- and micro-X-ray absorption near-edge structure spectroscopy confirmed that Se was mainly retained as reduced/stable species [Se(IV), organic Se, and Se(0)]. This study provides direct evidence for FGD WW Se retention in water-saturated soil via the transformation of oxidized Se into reduced/stable forms.

Industrial wastewater from the flue gas desulfurization (FGD) process is characterized by the presence of trace elements of concern, such as selenium (Se) and boron (B) and relatively high salinity. To simulate treatment that FGD wastewater undergoes during transport through soils in subsurface treatment systems, a column study (140-d duration) was conducted with native Kansas soil and saline FGD wastewater, containing high Se and B concentrations (170 μg/L Se and 5.3 mg/L B) and negligible arsenic (As) concentration (∼1.2 μg/L As). Se, B, and As, and dissolved organic carbon concentrations and organic matter spectroscopic properties were measured in the influent and outflow. Influent Se concentrations were reduced by only ∼half in all treatments, and results suggest that Se sorption was inhibited by high salinity of the FGD wastewater. By contrast, relative concentrations (C/C) of B in the outflow were typically <10%, suggesting that B sequestration may have been enhanced by higher salinity. Unexpected elevated As concentrations in the outflow (at >150 μg/L in the treatment with labile organic carbon addition) suggest that soils not previously known to be geogenic arsenic sources have the potential to release As to groundwater in the presence of high salinity wastewater and under reducing conditions.