Characterization of medium and small-scale gold processing operations, wastewaters, and tailings in the Arequipa region of Peru.

Gold cyanidation facilities in the Arequipa Region of Peru are challenged by the availability and quality of water for processing in an arid environment. The facilities reuse decant water which recycles residual cyanide but also undesirable constituents. To understand the impact of intensive water recycling on cyanide and metals concentrations, we collected barren water, decant water, and tailings samples from six gold cyanidation facilities with ore capacities of 10-430 tons per day. Processing facilities in Arequipa recycle all effluents, with decant waters making up 58 ± 11 % of process waters. Decant water contained non-target metals: copper (394 ± 161 mg/L), iron (59 ± 34 mg/L), and zinc (74 ± 42 mg/L). In addition, decant water mean free and complexed cyanide concentrations were 534 ± 129 mg/L and 805 ± 297 mg/L, respectively. Complexed cyanide concentrations remained more constant than free cyanide concentrations with 786 ± 299 mg/L for barren water and 805 ± 297 mg/L for decant water. Cyanide mass balances showed between 21 % and 42 % of unaccounted free cyanide from the start of gold cyanidation and discharge to the tailings storage facility (TSF). Free cyanide estimated losses due to volatilization were 0.8 kg and 2.5 kg of hydrogen cyanide per ton of ore processed at barren water pH of 10.1 and 9.7. Together these results indicate two acute hazards: 1) volatilization of free cyanide during processing and 2) loading and retention of cyanides and metals into TSFs. This study elucidates the extent of uncontrolled vapor phase cyanide release during gold processing operation and contaminant concentrations in the tailings storage facilities. The data highlights the need for improvement oversight, accountability, and regulation of gold processing facilities practicing intensive recycling and zero discharge.

Photosynthetic pretreatment increases membrane-based rejection of boron and arsenic.

The metalloids boron and arsenic are ubiquitous and difficult to remove during water treatment. As chemical pretreatment using strong base and oxidants can increase their rejection during membrane-based nanofiltration (NF), we examined a nature-based pretreatment approach using benthic photosynthetic processes inherent in a unique type of constructed wetland to assess whether analogous gains can be achieved without the need for exogenous chemical dosing. During peak photosynthesis, the pH of the overlying clear water column above a photosynthetic microbial mat (biomat) that naturally colonizes shallow, open water constructed wetlands climbs from circumneutral to approximately 10. This biological increase in pH was reproduced in a laboratory bioreactor and resulted in analogous increases in NF rejection of boron and arsenic that is comparable to chemical dosing. Rejection across the studied pH range was captured using a monoprotic speciation model. In addition to this mechanism, the biomat accelerated the oxidation of introduced arsenite through a combination of abiotic and biotic reactions. This resulted in increases in introduced arsenite rejection that eclipsed those achieved solely by pH. Capital, operation, and maintenance costs were used to benchmark the integration of this constructed wetland against chemical dosing for water pretreatment, manifesting long-term (sub-decadal) economic benefits for the wetland-based strategy in addition to social and environmental benefits. These results suggest that the integration of nature-based pretreatment approaches can increase the sustainability of membrane-based and potentially other engineered treatment approaches for challenging water contaminants.

A hybrid catalytic hydrogenation/membrane distillation process for nitrogen resource recovery from nitrate-contaminated waste ion exchange brine.

Ion exchange is widely used to treat nitrate-contaminated groundwater, but high salt usage for resin regeneration and management of waste brine residuals increase treatment costs and add environmental burdens. Development of palladium-based catalytic nitrate treatment systems for brine treatment and reuse has showed promising activity for nitrate reduction and selectivity towards the N2 over the alternative product ammonia, but this strategy overlooks the potential value of nitrogen resources. Here, we evaluated a hybrid catalytic hydrogenation/membrane distillation process for nitrogen resource recovery during treatment and reuse of nitrate-contaminated waste ion exchange brines. In the first step of the hybrid process, a Ru/C catalyst with high selectivity towards ammonia was found to be effective for nitrate hydrogenation under conditions representative of waste brines, including expected salt buildup that would occur with repeated brine reuse cycles. The apparent rate constants normalized to metal mass (0.30 ± 0.03 mM min-1 gRu-1 under baseline condition) were comparable to the state-of-the-art bimetallic Pd catalyst. In the second stage of the hybrid process, membrane distillation was applied to recover the ammonia product from the brine matrix, capturing nitrogen as ammonium sulfate, a commercial fertilizer product. Solution pH significantly influenced the rate of ammonia mass transfer through the gas-permeable membrane by controlling the fraction of free ammonia species (NH3) present in the solution. The rate of ammonia recovery was not affected by increasing salt levels in the brine, indicating the feasibility of membrane distillation for recovering ammonia over repeated reuse cycles. Finally, high rates of nitrate hydrogenation (apparent rate constant 1.80 ± 0.04 mM min-1 gRu-1) and ammonia recovery (overall mass transfer coefficient 0.20 m h-1) with the hybrid treatment process were demonstrated when treating a real waste ion exchange brine obtained from a drinking water utility. These findings introduce an innovative strategy for recycling waste ion exchange brine while simultaneously recovering potentially valuable nitrogen resources when treating contaminated groundwater.

Physicochemical characterization of solute retention in solvent resistant nanofiltration: the effect of solute size, polarity, dipole moment, and solubility parameter.

Growing interest in nanofiltration for solvent purification requires a fundamental understanding of the physicochemical mechanisms of solute retention in organic solvent nanofiltration. In this study, the retention of a similar series of azo dyes with approximately similar molar mass (around 350 Da) by four nanofiltration membranes was studied. The membranes used are commercially available polymeric nanofiltration membranes with molecular weight cutoff between 150 and 300 Da (DuraMem150, StarMem122, NF270 and Desal-Dk). In order to correlate the retention with the size of the molecules, which is assumed to be one of the main factors that determines the retention, use was made of different parameters for the molecular size: molar mass, the Stokes diameter, the equivalent molar diameter, and the cavity surface in methanol and ethanol. All parameters were calculated by using molecular dynamics simulations. For each size parameter, the correlation with retention in nanofiltration experiments was calculated. For the StarMem122 membrane, zero retentions were observed due to the swelling of the membrane and pore size enlargement in methanol and ethanol. For the three other membranes, a fairly good correlation of the retention with the size could only be observed if the size difference between compounds is sufficiently large. Two other factors were studied by using molecular dynamics, i.e., the polarity of the molecule and the electron density of the molecule. The importance of these factors depends on the structure of the molecule as well as the functional groups of the polymer. A very good correlation has been observed for retention of dyes versus their dipole moment. Finally, the effect of solubility parameters of dyes on their retention did not show any significant effect.