A screening method for preliminary assessment of risk to groundwater from land-applied chemicals

A simple mathematical model for initial screening is presented that can aid in evaluating the relative risk to groundwater from applying nonpolar synthetic organic chemicals to soil. The basic premise is that the magnitude of the quotient of the chemical concentration of the water entering the aquifer and the maximum allowable concentration (as established by EPA or Health Departments) represents the health risk of a chemical. The chemical concentration of the soil water is estimated based on conservative, simplifying assumptions and requires only readily available data such as: basic soil properties (organic matter and saturated hydraulic conductivity), organic chemical properties (octanol-water partition coefficient and degradation rate) and environmental factors (recharge rate and depth to groundwater).The methodology was applied to assess the relative risk of organic chemicals in municipal sewage sludge and pesticides applied to agricultural land. The results are realistic.     

Application of a minicolumn detection method for screening spices for aflatoxin

The minicolumn of Holaday and Lansden was modified by increasing the height of neutral alumina and including a layer of anhydrous sodium sulphate. Using this procedure, aflatoxin was detected in 18 of 125 samples of black pepper, red pepper, ginger and turmeric. A few samples of each spice contained aflatoxin, although red pepper and turmeric showed the highest incidence. Aflatoxin B1 quantities ranged from 10 ug/kg to 120 ug/kg when estimated quantitatively by visual comparison with standards on thin-layer chromatography plates.     

A novel methodology for determining low-cost fine particulate matter street sweeping routes

This paper addresses the problem of low-cost PM10 (particulate matter with aerodynamic diameter < 10 microm) street sweeping route. In order to do so, only a subset of the streets of the urban area to be swept is selected for sweeping, based on their PM10 emission factor values. Subsequently, a low-cost route that visits each street in the set is computed. Unlike related problems of waste collection where streets must be visited once (Chinese or Rural Postman Problem, respectively), in this case, the sweeping vehicle route must visit each selected street exactly as many times as its number of street sides, since the vehicle can sweep only one street side at a time. Additionally, the route must comply with traffic flow and turn constraints. A novel transformation of the original arc routing problem into a node routing problem is proposed in this paper. This is accomplished by building a graph that represents the area to sweep in such a way that the problem can be solved by applying any known solution to the Traveling Salesman Problem (TSP). As a way of illustration, the proposed method was applied to the northeast area of the Municipality of Santiago (Chile). Results show that the proposed methodology achieved up to 37% savings in kilometers traveled by the sweeping vehicle when compared to the solution obtained by solving the TSP problem with Geographic Information Systems (GIS)--aware tools.     

Studies on arsenic transforming groundwater bacteria and their role in arsenic release from subsurface sediment

Ten different Gram-negative arsenic (As)-resistant and As-transforming bacteria isolated from As-rich groundwater of West Bengal were characterized to assess their role in As mobilization. 16S rRNA gene analysis confirmed the affiliation of these bacteria to genera Achromobacter, Brevundimonas, Rhizobium, Ochrobactrum, and Pseudoxanthomonas. Along with superior As-resistance and As-transformation abilities, the isolates showed broad metabolic capacity in terms of utilizing a variety of electron donors and acceptors (including As) under aerobic and anaerobic conditions, respectively. Arsenic transformation studies performed under various conditions indicated highly efficient As³⁺ oxidation or As⁵⁺ reduction kinetics. Genes encoding As³⁺ oxidase (aioA), cytosolic As⁵⁺ reductase (arsC), and As³⁺ efflux pump (arsB and acr3) were detected within the test isolates. Sequence analyses suggested that As homeostasis genes (particularly arsC, arsB, and acr3) were acquired by most of the bacteria through horizontal gene transfer. A strong correlation between As resistance phenotype and the presence of As³⁺ transporter genes was observed. Microcosm study showed that bacterial strain having cytosolic As⁵⁺ reductase property could play important role in mobilizing As (as As³⁺) from subsurface sediment.     

Concentrations and speciation of arsenic in groundwater polluted by warfare agents

Groundwater polluted with phenylarsenicals from former warfare agent deposits and their metabolites was investigated with respect to the behavior of relevant arsenic species. Depth profiles at the estimated source and at about 1 km downgradient from the source zone were sampled. The source zone is characterized by high total arsenic concentrations up to 16 mg L⁻¹ and is dominated by organic arsenic compounds. The concentrations in the downgradient region are much lower (up to 400 μg L⁻¹) and show a high proportion of inorganic arsenic species. Iron precipitation seems to be an effective mechanism to prevent dispersion of inorganic arsenic as well as phenylarsonic acid. Reductive conditions were observed in the deeper zone with predominant occurrence of trivalent arsenic species. The inorganic species are in redox equilibrium, whereas the phenylarsenic compounds have variable proportions. Methylphenylarsinic acid was identified in groundwater in traces which indicates microbial degradation activity.     

Optimized method for dissolved hydrogen sampling in groundwater

Dissolved hydrogen concentrations are used to characterize redox conditions of contaminated aquifers. The currently accepted and recommended bubble strip method for hydrogen sampling (Wiedemeier et al., 1998) requires relatively long sampling times and immediate field analysis. In this study we present methods for optimized sampling and for sample storage. The bubble strip sampling method was examined for various flow rates, bubble sizes (headspace volume in the sampling bulb) and two different H2 concentrations. The results were compared to a theoretical equilibration model. Turbulent flow in the sampling bulb was optimized for gas transfer by reducing the inlet diameter. Extraction with a 5 mL headspace volume and flow rates higher than 100 mL/min resulted in 95-100% equilibrium within 10-15 min. In order to investigate the storage of samples from the gas sampling bulb gas samples were kept in headspace vials for varying periods. Hydrogen samples (4.5 ppmv, corresponding to 3.5 nM in liquid phase) could be stored up to 48 h and 72 h with a recovery rate of 100.1+/-2.6% and 94.6+/-3.2%, respectively. These results are promising and prove the possibility of storage for 2-3 days before laboratory analysis. The optimized method was tested at a field site contaminated with chlorinated solvents. Duplicate gas samples were stored in headspace vials and analyzed after 24 h. Concentrations were measured in the range of 2.5-8.0 nM corresponding to known concentrations in reduced aquifers.     

A method for the in-situ determination of dissolved methane in groundwater in shallow aquifers

Dissolved methane in groundwater has potential for use as a tracer of waste contamination in aquifers, and is itself a contaminant of concern because of potential explosion hazards following pumping of groundwater to the surface. A technique is described and evaluated for in-situ determination of the variation in concentration of dissolved methane with depth in shallow aquifers. The technique uses diffusion cells (small diameter teflon tubes) buried in boreholes and connected to the surface by small diameter nylon access tubes. A stream of gas is passed through the cells until a steady flux of methane is obtained. The steady state flux can then be related to concentration or partial pressure of methane in groundwater in contact with the cell, from prior laboratory calibration. Some temperature compensation is required.Two strings of cells with nylon access tubes for gas purging have been emplaced in permeable grout within boreholes drilled in sand a aquifer. The depth-related concentrations of dissolved methane found using these cells compare reasonably well with less precise data obtained by sampling of conventional boreholes situated adjacent to each string of cells.     

Removal of arsenic from groundwater by granular titanium dioxide adsorbent

A novel granular titanium dioxide (TiO2) was evaluated for the removal of arsenic from groundwater. Laboratory experiments were carried out to investigate the adsorption capacity of the adsorbent and the effect of anions on arsenic removal. Batch experimental results showed that more arsenate [As(V)] was adsorbed on TiO2 than arsenite [As(III)] in US groundwater at pH 7.0. The adsorption capacities for As(V) and As(III) were 41.4 and 32.4 mgg(-1) TiO2, respectively. However, the adsorbent had a similar adsorption capacity for As(V) and As(III) (approximately 40 mgg(-1)) when simulated Bangladesh groundwater was used. Silica (20 mgl(-1)) and phosphate (5.8 mgl(-1)) had no obvious effect on the removal of As(V) and As(III) by TiO2 at neutral pH. Point-of-entry (POE) filters containing 3 l of the granular adsorbent were tested for the removal of arsenic from groundwater in central New Jersey, USA. Groundwater was continuously passed through the filters at an empty bed contact time (EBCT) of 3 min. Approximately 45,000 bed volumes of groundwater containing an average of 39 microgl(-1) of As(V) was treated by the POE filter before the effluent arsenic concentration increased to 10 microgl(-1). The total treated water volumes per weight of adsorbent were about 60,000 l per 1 kg of adsorbent. The field filtration results demonstrated that the granular TiO2 adsorbent was very effective for the removal of arsenic in groundwater.     

Removal of arsenic from contaminated groundwater by solar-driven membrane distillation

Experimental investigations were carried out on removal of arsenic from contaminated groundwater by employing a new flat-sheet cross flow membrane module fitted with a hydrophobic polyvinylidenefluoride (PVDF) microfiltration membrane. The new design of the solar-driven membrane module in direct contact membrane distillation (DCMD) configuration successfully produced almost 100 per cent arsenic-free water from contaminated groundwater in a largely fouling-free operation while permitting high fluxes under reduced temperature polarization. For a feed flow rate of 0.120 m³/h, the 0.13 μm PVDF membrane yielded a high flux of 74 kg/(m² h) at a feed water temperature of 40 °C and, 95 kg/m² h at a feed water temperature of 60 °C. The encouraging results show that the design could be effectively exploited in the vast arsenic-affected rural areas of South-East Asian countries blessed with abundant sunlight particularly during the critical dry season.     

Geochemistry of high arsenic groundwater in Chia-Nan plain, Southwestern Taiwan: possible sources and reactive transport of arsenic

Major ion, trace element, and stable isotope analyses were performed on groundwater samples collected during November 2005 and 2006 in Chia-Nan plain of southwestern Taiwan to examine As mobilization in aquifers. The high concentrations of As, Fe and Mn in the groundwater is consistent with low Eh values (under moderately reduced state). Moreover, the observed Na/Cl and SO(4)/Cl molar ratios in groundwater demonstrate the influence of seawater intrusion. Seawater intrusion could provide required electron acceptors (i.e., SO(4)) for bacterial sulfate reduction and promote reducing conditions that are favorable for As mobilization. The concurrent increases in the concentrations of Fe and Mn from 2005 to 2006 may be caused by bacterial Fe(III) and Mn(IV) reduction. Geochemical modeling demonstrate that As(III) is the dominant As species and the presence of Fe-bearing carbonates, sulfides, and oxide phases may locally act as potential sinks for As. Mud volcano fluids were also collected and analyzed to assess the possible source of As in the Chia-Nan plain groundwater. The oxygen and hydrogen isotopic signatures indicate that the As-rich mud volcano fluids may have been modified by chemical exchange with (18)O-rich crustal rocks and possibly originated from mixing of deep brines with circulating meteoric water. Thus As in the Chia-Nan plain groundwater may have been evolved from deep crustal fluids or rock sources. The hydrogeochemistry and widespread As enrichment in groundwater of Chia-Nan plain result from multiple processes, e.g., de-watering of deep crustal fluids, seawater intrusion, and biogeochemical cycling of Fe, As, and S in alluvial sediments.     

Removal of arsenic from groundwater by micellar-enhanced ultrafiltration (MEUF)

The removal characteristics of arsenate using micellar-enhanced ultrafiltration (MEUF) were investigated. Among four different cationic surfactants used, hexadecylpyridinium chloride (CPC) showed the highest removal efficiency of arsenic (96%), and the removal efficiency with hexadecyltrimethylammonium bromide (CTAB) was 94%. But the removal efficiency with benzalkonium chloride (BC) was the lowest (57%) due to higher critical micelle concentration (CMC) of BC than those of other surfactants. Over 80% of arsenic was removed with octadecylamine acetate (ODA). On the effect of solution pH on the arsenic removal, since the valance of arsenate decreases from trivalent to monovalent as pH decreases, the removal was reduced at lower pH. The presence of 0.45mM of nitrate and 0.01mM of phosphate reduced the removal efficiency by 5-8%. This decrease was because of the competition between the arsenate, nitrate and phosphate for the binding sites of the surfactant micelle. Similar decrease in the removal of arsenate was observed with CPC, CTAB and ODA in the presence of these anions. In cross-flow filtration, the removal efficiency of arsenic was similar to that in the dead-end system. However, the decline in flux was less than that in dead-end filtration. In order to lower the concentration of the surfactant in the effluent, the effluent was treated with powdered activated carbon (PAC) before discharging to the environment. Over 98% surfactant was removed with 1gl(-1) of PAC. In conclusions, the MEUF is considered as a feasible process using CPC or CTAB to remove the arsenate from groundwater compared with the other solid based adsorbent processes.     

A modified in-vitro method to assess bioavailable arsenic in pesticide-applied soils

An incubation study was designed to modify the existing in vitro methods to increase the accuracy in estimation of bioavailable arsenic in pesticide-applied soils. In addition to simulating arsenic dissolution in gastric and intestinal solutions, absorbtion by the intestinal membrane was also mimicked using iron-oxide coated filter paper strips inserted in nylon bags. The in vitro experiments were sequentially performed in two phases, namely, the stomach phase and the absorbed-intestinal phase. Arsenic extraction in the in vitro absorbed intestinal phase increased, thereby making it more comparable to the potential in vivo arsenic pool. While animal studies are needed to verify the in vitro results, preliminary data indicate that this modified method may be able to improve site-specific bioavailability predictions in arsenic-contaminated soils.     

Mobilization of arsenic from subsurface sediments by effect of bicarbonate ions in groundwater

Arsenic leaching by bicarbonate ions has been investigated in this study. Subsurface sediment samples from Bangladesh were treated with different carbonate and bicarbonate ions and the results demonstrate that the arsenic leaching efficiency of the carbonate solutions decreased in the order of Na2CO3>NaHCO3>BaCO3>MnCO3. Sodium carbonate and bicarbonate ions extracted arsenic most efficiently; Na2CO3 leached maximum 118.12 microg/l of arsenic, and NaHCO3, 94.56 microg/l of arsenic from the Ganges delta sediments after six days of incubation. The arsenic concentrations extracted in the batch experiments correlated very well with the bicarbonate concentrations. The kinetics study of arsenic release indicates that arsenic-leaching rate increased with reaction time in bicarbonate solutions. Bicarbonate ions can extract arsenic from sediment samples in both oxic and anoxic conditions. A linear relationship found between arsenic contents in core samples and those in leachates suggests that dissolved arsenic concentration in groundwater is related to the amount of arsenic in aquifer sediments. In batch experiment, bicarbonate solutions effectively extracted arsenic from arsenic adsorbed iron oxyhydroxide, reflecting that bicarbonate solutions may mobilize arsenic from iron and manganese oxyhydroxide in sediments that are ubiquitous in subsurface core samples. Carbonate ion may form complexes on the surface sites of iron hydroxide and substitute arsenic from the surface of minerals and sediments resulting in release of arsenic to groundwater. Like in the batch experiment, arsenic and bicarbonate concentrations in groundwater of Bangladesh correlated very well. Therefore, bicarbonate leaching is presumed to be one important mechanism to mobilize arsenic in bicarbonate dominated reducing aquifer of Bangladesh and other parts of the world as well.     

纳滤膜技术在地下水除砷应用中的研究进展

砷污染突发事件的频发严重威胁着地下水饮用水水源的水质安全,加之饮用水控制标准的提高,就对饮用水除砷技术提出了更高的要求,而纳滤(NF)膜分离技术为饮用水除砷提供了新的思路。首先概述了地下水中砷的存在形态、化学性质以及我国高砷地下水地区分布,然后分析了NF膜特点、除砷机理与性能,系统地阐述了各种因素包括膜操作因素（操作压力、膜回收率、膜排布方式等）和原水水质因素（pH、水温、共存离子、共存有机物及砷浓度与砷价态等）,对NF膜除砷性能的影响。此外,对NF除砷的关键问题,如原水预处理、膜浓水处理、膜污染及其清洗等,也作了探讨。最后,总结了目前NF除砷应用中所面临的问题,探索性提出了NF膜技术在除砷应用中的研究方向。     

地下水中潜在危害有机物识别与筛选方法

针对地下水中频繁检出的各类有机物,运用理论方法定量计算污染物对地下水的危害系数,对有机物的污染调查、地下水污染防治具有一定的指导意义。为研究有机物对地下水的危害性,汇总了535项有机物,目前这些指标在国内外水质标准中均没给出标准值。从有机物的自身属性入手,假定所有物质处于相同的外界环境中,经过包气带吸附、降解、挥发等作用,分析其进入地下水的难易程度。利用美国环保局的软件EPI Suit4.10,获取了指标的有机碳吸附系数(Koc)、半衰期(DT50)和亨利常数(KH),并结合毒性参数基于健康的评价基准值,构建了污染物潜在危害参数体系。运用3种方法计算有机物的危害系数H、污染指数G和衰减系数K,对比3种计算结果,筛选出100项潜在危害有机物。分析表明,所筛选出的100项指标毒性较大、难挥发,并且有机物的Koc对污染指数(G)和衰减系数(K)的贡献比DT50、KH更大。     

Alternative low-cost process for large-scale production of Bacillus thuringiensis in a simple and novel culture system

Abstract

An industrial-scale, profitable method for production of the most widely used bioinsecticide, Bacillus thuringiensis (Bt), is challenging because of its widespread application. The aim of this study is to present a strategy to develop a low-cost, large-scale bioprocess to produce Bt H14.

This study was first focused on the design of a culture medium composed of economical and available components, such as glycerol and lysed Saccharomyces cerevisiae. The production goal of 1200 ITU was achieved using a medium composed of 20:20 g L^?1of glycerol:lysed yeast in batch cultures. Efforts were subsequently focused on the design of an appropriate culture system, and an original two-stage culture system was proposed. First, yeast (the primary component of the culture medium) are cultivated using a minimal mineral medium and lysed, and in the second stage, Bt is cultivated in the same bioreactor using the lysed yeasts as culture medium (supplemented with a feeding pulse of 10 g L^?1 glycerol). This system was called fed batch one pot (FOP). A new inoculation strategy is also presented in this study, since these Bt cultures were inoculated directly with heat pre-treated spores instead of vegetative bacteria to facilitate the bioprocess. This study was developed from the laboratory to production-scale bioreactors (measuring from 500 mL to 2500 L), and the efficiency of the proposed strategy was evident in LD₅₀ tests results, achieving 1796 ITU in large-scale processes. Both the use of non-conventional sources and the process development for biomass production are important for cost-effective production of Bt-based insecticides in mosquito control projects.     

Co-contamination of arsenic and fluoride in the groundwater of unconsolidated aquifers under reducing environments

The co-contamination of arsenic (As) and fluoride (F⁻) in shallow aquifers is frequently observed worldwide, and the correlations between those contaminants are different according to the redox conditions. This study geochemically explores the reasons for the co-contamination and for the redox-dependent correlations by investigating the groundwater of an alluvial aquifer in Korea. Geochemical signatures of the groundwater in the study area show that the As concentrations are enriched by the reductive dissolution of Fe-(hydr)oxides, and the correlations between As and F⁻ concentrations are poor comparatively to those observed in the oxidizing aquifers. However, F⁻ concentrations are strongly dependent on pH. Desorption/adsorption experiments using raw soils and citrate-bicarbonate-dithionite treated soils indicated that Fe-(hydr)oxides are the important As and F⁻ hosts causing the co-contamination phenomenon. The weaker correlation between F⁻ and As in reducing aquifers is likely to be associated with sulfate reduction, which removes As from groundwater without changing the F⁻ concentration.     

Evaluating a drinking-water waste by-product as a novel sorbent for arsenic

Arsenic (As) carcinogenicity to humans and other living organisms has promulgated extensive research on As treatment technologies with varying levels of success; generally, the most efficient methods come with a significantly higher cost burden and they usually perform better in removing As(V) than As(III) from solution. In the reported study, a novel sorbent, a waste by-product of the drinking-water treatment process, namely, drinking-water treatment residuals (WTRs) were evaluated for their ability to adsorb both As(V) and As(III). Drinking-WTRs can be obtained free-of-charge from drinking-water treatment plants, and they have been successfully used to reduce soluble phosphorus (P) concentrations in poorly P-sorbing soils. Phosphate and arsenate molecules have the same tetrahedral geometry, and they chemically behave in a similar manner. We hypothesized that the WTRs would be effective sorbents for both As(V) and As(III) species. Two WTRs (one Fe- and one Al-based) were used in batch experiments to optimize the maximum As(V) and As(III) sorption capacities, utilizing the effects of solid:solution ratios and reaction kinetics. Results showed that both WTRs exhibited high affinities for soluble As(V) and As(III), exhibiting Freundlich type adsorption with no obvious plateau after 2-d of reaction (15000 mg kg-1). The Al-WTR was highly effective in removing both As(V) and As(III), although As(III) removal was much slower. The Fe-WTR showed greater affinity for As(III) than for As(V) and reached As(III) sorption capacity levels similar to those obtained with the Al-WTR-As(V) system (15000 mg kg-1). Arsenic sorption kinetics were biphasic, similar to what has been observed with P sorption by the WTRs. Minimal (<3%) desorption of sorbed As(III) and As(V) was observed, using phosphate as the desorbing ligand. Dissolved Fe2+ concentrations measured during As(III) sorption were significantly correlated (r2=0.74, p<0.005) with the amount of As(III) sorbed by the Fe-WTR. Lack of correlation between Fe2+ in solution and sorbed As(V) (r2=0.2) suggests reductive dissolution of the Fe-WTR mediating As(III) sorption. Results show promising potential for the WTRs in irreversibly retaining As(V) and As(III) that should be further tested in field settings.