Predicting contaminant adsorption in black carbon (biochar)-amended soil for the veterinary antimicrobial sulfamethazine.

Commercial hardwood biochars ranging in N2 specific surface area of 0.1-427 m(2) · g(-1) were added to an agricultural soil at 0, 1, or 2% levels to determine whether they would predictably reduce the pore water concentration of sulfamethazine (SMT). The soil and biochar-soil mixtures were preweathered under mild (2 d, 20 °C) or more severe (28 d, 40 °C) conditions before spiking. The carbon-normalized biochar-water distribution coefficient (KBC) of the biochars varied by a factor of up to 10(4), depending on biochar properties and SMT concentration. Except for the fast-pyrolysis biochar, KBC greatly exceeded the soil organic carbon-water distribution coefficient KOC. Sorption in the mixtures increased as expected with biochar and dose. However, sorption was dramatically overpredicted (by up to 10(2.5)) by the sum of sorption to the individual components, indicating a strong weathering effect even under the mild conditions. The soil-subtracted weathered biochar-water isotherms were more linear, and the KBC values approached or lay within the range of KOC values reported for SMT in 19 soils. Biochars both in intimate contact with soil and placed in a membrane bag suspended in the solution showed reduced N2-B.E.T. surface area after weathering, implicating fouling of the biochar surface by humic substances transferred through water. The results indicate that only highly surfaceous, carbonaceous biochars would be useful for stabilizing soil contaminated with compounds such as SMT. They also suggest that weathering may attenuate the contribution of native (environmental) black carbon to sorption of such compounds in soils and sediments.

Contaminants of emerging concern in the urban aquifers of Barcelona: Do they hamper the use of groundwater?

Urban aquifers are an alternative to obtain freshwater, but they are frequently polluted by contaminants of emerging concern (CECs). Therefore, there is a need to ascertain whether CECs are a water management challenge as they might limit the use of groundwater as safe drinking water even at ng L-1 concentration levels. To answer this question, it is required to evaluate human health-risk effects of measured CECs in the groundwater and to understand their behaviour at a field-scale. This study compiles data about the presence of CECs in the aquifers of Barcelona and its metropolitan area, evaluates health risk effects of measured CECs in the groundwater and presents approaches implemented to identify and quantify the coupled hydro-thermo-chemical processes that govern their fate in the subsurface. Some CECs might be harmful to humans, such as 5-methyl-1H-benzotriazole and the pharmaceuticals azithromycin valsartan, valsartan acid, lamotrigine, gabapentin, venlafaxine and lidocaine, which show very high to intermediate health risk effects. The number of harmful CECs and the level of their hazard increase from the groups of adults and 14-18 years old teens to the groups of 4-8 years old and 1-2 years old children. Thus, some CECs can limit the use of groundwater in Barcelona as potential drinking water source. Finally, knowledge gaps in understanding the integration of these processes into urban water resources management plans are identified, which will help to define groundwater potential uses and to assure the adequate protection of the human health and the environment.

Transport and removal of stormwater vehicle-related mobile organic contaminants in geomedia-amended sand columns.

Green infrastructure drainage systems are innovative treatment units that capture and treat stormwater. Unfortunately, highly polar contaminants remain challenging to remove in conventional biofilters. To overcome treatment limitations, we assessed the transport and removal of stormwater vehicle-related organic contaminants with persistent, mobile, and toxic (in short: PMTs) properties, such as 1H-benzotriazole, NN'-diphenylguanidine, and hexamethoxymethylmelamine (PMT precursor), using batch experiments and continuous-flow sand columns amended with pyrogenic carbonaceous materials, like granulated activated carbon (GAC) or wheat-straw derived biochar. Our results indicated that all investigated contaminants were subjected to nonequilibrium interactions in sand-only and geomedia-amended columns, with kinetic effects upon transport. Experimental breakthrough curves could be well described by a one-site kinetic transport model assuming saturation of sorption sites, which we inferred could occur due to dissolved organic matter fouling. Furthermore, from both batch and column experiments, we found that GAC could remove contaminants significantly better than biochar with higher sorption capacity and faster sorption kinetics. Hexamethoxymethylmelamine, with the lowest organic carbon-water partition coefficient (KOC) and largest molecular volume among target chemicals, exhibited the lowest affinity in both carbonaceous adsorbents based on estimated sorption parameters. Results suggest that sorption of investigated PMTs was likely driven by steric and hydrophobic effects, and coulombic and other weak intermolecular forces (e.g., London-van der Waals, H-bonding). Results from extrapolating our data to a 1-m depth geomedia-amended sand filter suggested that GAC and biochar could enhance the removal of organic contaminants in biofilters and last for more than one decade. Overall, our work is the first to study treatment alternatives for NN'-diphenylguanidine and hexamethoxymethylmelamine, and contributes to better PMT contaminant removal strategies in environmental applications.

Potential of low-enthalpy geothermal energy to degrade organic contaminants of emerging concern in urban groundwater.

Low-enthalpy geothermal energy (LEGE) is a carbon-free and renewable source to provide cooling and heating to infrastructures (e.g. buildings) by exchanging their temperature with that of the ground. The exchange of temperature modifies the groundwater temperature around LEGE installations, which may contribute to enhancing the capacity of aquifers to degrade organic contaminants of emerging concern (OCECs), whose presence is significantly increasing in urban aquifers. Here, we investigate the impact of LEGE on OCECs and their bioremediation potential through numerical modelling of synthetic and real-based cases. Simulation results demonstrate that: (i) LEGE facilities have the potential to noticeably modify the concentrations of OCECs; and (ii) the final impact depends on the design of the facility. This study suggests that optimized LEGE facility designs could contribute to the degradation of OCECs present in urban aquifers, thus improving groundwater quality and increasing its availability in urban areas.

Use of pilot-scale geomedia-amended biofiltration system for removal of polar trace organic and inorganic contaminants from stormwater runoff.

Stormwater runoff capture and groundwater recharge can provide a sustainable means of augmenting the local water resources in water-stressed cities while simultaneously mitigating flood risk, provided that these processes do not compromise groundwater quality. We developed and tested for one year an innovative pilot-scale stormwater treatment train that employs cost-effective engineered geomedia in a continuous-flow unit-process system to remove contaminants from urban runoff during aquifer recharge. The system consisted of an iron-enhanced sand filter for phosphate removal, a woodchip bioreactor for nitrate removal coupled to an aeration step, and columns packed with different configurations of biochar- and manganese oxide-containing sand to remove trace metals and persistent, mobile, and toxic trace organic contaminants. During conditioning with authentic stormwater runoff over an extended period (8 months), the woodchip bioreactor removed 98% of the influent nitrate (9 g-N m-3 d-1), while phosphate broke through the iron-enhanced sand filter. During the challenge test (4 months), geomedia removed more than 80% of the mass of metals and trace organic compounds. Column hydraulic performance was stable during the entire study, and the weathered biochar and manganese oxide were effective at removing trace organic contaminants and metals, respectively. Under conditions likely encountered in the field, sustained nutrient removal is probable, but polar organic compounds such as 2,4-D could breakthrough after about a decade for conditions at the study site.

Speciation of the ionizable antibiotic sulfamethazine on black carbon (biochar).

Adsorption of ionizable compounds by black carbon is poorly characterized. Adsorption of the veterinary antibiotic sulfamethazine (SMT; a.k.a., sulfadimidine; pK(a1) = 2.28, pK(a2) = 7.42) on a charcoal was determined as a function of concentration, pH, inorganic ions, and organic ions and molecules. SMT displayed unconventional adsorption behavior. Despite its hydrophilic nature (log K(ow) = 0.27), the distribution ratio K(d) at pH 5, where SMT(0) prevails, was as high as 10(6) L kg(-1), up to 10(4) times greater than literature reported K(oc). The K(d) decreases at high and low pH but not commensurate with the decline in K(ow) of the ionized forms. At pH 1, where SMT(+) is predominant and the surface is positive, a major driving force is π-π electron donor-acceptor interaction of the protonated aniline ring with the π-electron rich graphene surface, referred to as π(+)-π EDA, rather than ordinary electrostatic cation exchange. In the alkaline region, where SMT(-) prevails and the surface is negative, adsorption is accompanied by near-stoichiometric proton exchange with water, leading to the release of OH(-) and formation of an exceptionally strong H-bond between SMT(0) and a surface carboxylate or phenolate, classified as a negative charge-assisted H-bond, (-)CAHB. At pH 5, SMT(0) adsorption is accompanied by partial proton release and is competitive with trimethylphenylammonium ion, signifying contributions from SMT(+) and/or the zwitterion, SMT(±), which take advantage of π(+)-π EDA interaction and Coulombic attraction to deprotonated surface groups. In essence, both pK(a1) and pK(a2) increase, and SMT(±) is stabilized, in the adsorbed relative to the dissolved state.

Polymer-clay composite geomedia for sorptive removal of trace organic compounds and metals in urban stormwater.

Functionalized polymer-clay composites were developed and characterized as engineered geomedia for trace contaminant removal during infiltration of urban runoff. Montmorillonite clays were functionalized with either poly(diallyldimethylammonium) chloride (PDADMAC) or poly(4-vinylpyridine-co-styrene) (PVPcoS) to enhance organic compound sorption using a simple, scalable synthesis method. Seven representative trace organic compounds and six trace metals were employed to assess the performance of the polymer-clay composites relative to biochar (i.e., an adsorbent proposed for similar purposes) in batch sorption and column studies under simulated stormwater conditions. Contaminant and geomedia electrostatic and hydrophobic interactions, and the presence of natural organic matter (NOM) affected sorption. In batch studies, polymer-clay composites exhibited similar performance to biochar for perfluoroalkyl substance removal, but had lower affinity for polar pesticides and tris(2-chloroethyl) phosphate. Oxyanion removal was greatest for positively-charged PDADMAC-clay composites (particularly Cr[VI]), while PVPcoS-clay composites removed over 95% of Ni, Cd, and Cu. NOM decreased removal of all organic compounds, but increased trace metal removal on clay composites due to sorption of NOM-complexed metals. Polymer-clay composite-amended columns best removed oxyanions, while biochar-amended columns exhibited superior removal for all trace organics. At 3 wt% geomedia-sand loading, clay composites exhibited significantly higher saturated hydraulic conductivity than biochar, which is advantageous when clogging is a concern or when rapid infiltration is needed. Under typical urban stormwater conditions, the clay composites will remove contaminants for at least 20-30 years before regeneration or replacement is needed.

Evaluation of pilot-scale biochar-amended woodchip bioreactors to remove nitrate, metals, and trace organic contaminants from urban stormwater runoff.

Stormwater is increasingly being valued as a freshwater resource in arid regions and can provide opportunities for beneficial reuse via aquifer recharge if adequate pollutant removal can be achieved. We envision a multi-unit operation approach to capture, treat, and recharge (CTR) stormwater using low energy, cost-effective technologies appropriate for larger magnitude, less frequent events. Herein, we tested nutrient, metal, and trace organic contaminant removal of a pilot-scale CTR system in the laboratory using biochar-amended woodchip bioreactors following eight months of aging under field conditions with exposure to real stormwater. Replicate columns with woodchips and biochar (33% by weight), woodchips and straw, or woodchips only were operated with continuous, saturated flow for eight months using water from a watershed that drained an urban area consisting of residential housing and parks in Sonoma, California. After aging, columns were challenged for five months by continuous exposure to synthetic stormwater amended with 50 µg L-1 of six trace organic contaminants (i.e., fipronil, diuron, 1H-benzotriazole, atrazine, 2,4-D, and TCEP) and five metals (Cd, Cu, Ni, Pb, Zn) frequently detected in stormwater in order to replicate the treatment unit operation of a CTR system. Throughout the eight-month aging and five-month challenge experiment, nitrate concentrations were below the detection limit after treatment (i.e., <0.05 mg N L-1). The removal efficiencies for metals in all treatments were >80% for Ni, Cu, Cd, and Pb. For Zn, about 50% removal occurred in the woodchip-biochar systems while the other systems achieved about 20% removal. No breakthrough of the trace organic compounds was observed in any biochar-containing columns. Woodchip columns without biochar removed approximately 99% of influent atrazine and 90% of influent fipronil, but exhibited relatively rapid breakthrough of TCEP, 2,4-D, 1H-benzotriazole, and diuron. The addition of straw to the woodchip columns provided no significant benefit compared to woodchips alone. Due to the lack of breakthrough of trace organics in the biochar-woodchip columns, we estimated column breakthrough with a diffusion-limited sorption model. Results of the model indicate breakthrough for the trace organics would occur between 10,000 and 32,000 pore volumes. Under ideal conditions this could be equivalent to decades of service, assuming failure by other processes (e.g., clogging, biofouling) does not occur. These results indicate that multiple contaminants can be removed in woodchip-biochar reactors employed in stormwater treatment systems with suitable flow control and that the removal of trace organic contaminants is enhanced significantly by addition of biochar.