Rai S. Kookana

Environmental fate of alkylphenols and alkylphenol ethoxylates—a review

Alkylphenol ethoxylates (APEs) are widely used surfactants in domestic and industrial products, which are commonly found in wastewater discharges and in sewage treatment plant (STP) effluents. Degradation of APEs in wastewater treatment plants or in the environment generates more persistent shorter-chain APEs and alkylphenols (APs) such as nonylphenol (NP), octylphenol (OP) and AP mono- to triethoxylates (NPE1, NPE2 and NPE3). There is concern that APE metabolites (NP, OP, NPE1-3) can mimic natural hormones and that the levels present in the environment may be sufficient to disrupt endocrine function in wildlife and humans. The physicochemical properties of the APE metabolites (NP, NPE1-4, OP, OPE1-4), in particular the high K(ow) values, indicate that they will partition effectively into sediments following discharge from STPs. The aqueous solubility data for the APE metabolites indicate that the concentration in water combined with the high partition coefficients will provide a significant reservoir (load) in various environmental compartments. Data from studies conducted in many regions across the world have shown significant levels in samples of every environmental compartment examined. In the US, levels of NP in air ranged from 0.01 to 81 ng/m3, with seasonal trends observed. Concentrations of APE metabolites in treated wastewater effluents in the US ranged from < 0.1 to 369 microg/l, in Spain they were between 6 and 343 microg/l and concentrations up to 330 microg/l were found in the UK. Levels in sediments reflected the high partition coefficients with concentrations reported ranging from < 0.1 to 13,700 microg/kg for sediments in the US. Fish in the UK were found to contain up to 0.8 microg/kg NP in muscle tissue. APEs degraded faster in the water column than in sediment. Aerobic conditions facilitate easier further biotransformation of APE metabolites than anaerobic conditions.

Occurrence and fate of hormone steroids in the environment.

Hormone steroids are a group of endocrine disruptors, which are excreted by humans and animals. In this paper, we briefly review the current knowledge on the fate of these steroids in the environment. Natural estrogenic steroids estrone (E1), 17beta-estradiol (E2) and estriol (E3) all have a solubility of approximately 13 mg/l, whereas synthetic steroids 17alpha-ethynylestradiol (EE2) and mestranol (MeEE2) have a solubility of 4.8 and 0.3 mg/l, respectively. These steroids have a moderate binding on sediments and are reported to degrade rapidly in soil and water. Estrogenic steroids have been detected in effluents of sewage treatment plants (STPs) in different countries at concentrations ranging up to 70 ng/l for E1, 64 ng/l for E2, 18 ng/l for E3 and 42 ng/l for EE2. E2 concentrations in river waters from Japan, Germany, Italy and the Netherlands ranged up to 27 ng/l. In addition, E2 concentrations ranging from 6 to 66 ng/l have also been measured in mantled karst aquifers in northwest Arkansas. This contamination of ground water has been associated with poultry litter and cattle manure waste applied on the land. Although hormone steroids have been detected at a number of sources worldwide, currently, there is limited data on the environmental behaviour and fate of these hormone steroids in different environmental media. Consequently, the exposure and risk associated with these chemicals are not adequately understood.

Biochar application to soil: agronomic and environmental benefits and unintended consequences.

Abstract Biochar is increasingly being recognized by scientists and policy makers for its potential role in carbon sequestration, reducing greenhouse gas emissions, renewable energy, waste mitigation, and as a soil amendment. The published reviews on biochar application to soil have so far focused mainly on the agronomic benefits, and have paid little attention to the potential unintended effects. The purpose of this chapter is to provide a balanced perspective on the agronomic and environmental impacts of biochar amendment to soil. The chapter highlights the physical and chemical characteristics of biochar, which can impact on the sorption, hence efficacy and biodegradation, of pesticides. As a consequence, weed control in biochar-amended soils may prove more difficult as preemergent herbicides may be less effective. Since biochars are often prepared from a variety of feedstocks (including waste materials), the potential introduction of contaminants needs to be considered before land application. Metal contaminants, in particular, have been shown to impact on plant growth, and soil microbial and faunal communities. Biochar has also been shown to influence a range of soil chemical properties, and rapid changes to nutrient availability, pH, and electrical conductivity need to be carefully considered to avoid unintended consequences for productivity. This chapter highlights some key areas of research which need to be completed to ensure a safe and sustainable use of biochar. In particular, understanding characteristics of biochars to avoid ecotoxicological impacts, understanding the effects of biochar on nutrient and contaminant behavior and transport, the effects of aging and the influence of feedstock and pyrolysis conditions on key properties are some of the areas that require attention.

SORPTION AND DEGRADATION OF SELECTED FIVE ENDOCRINE DISRUPTING CHEMICALS IN AQUIFER MATERIAL

Sorption and degradation of the five selected endocrine disrupting chemicals (EDCs) including bisphenol A (BPA), 17 beta-estradiol (E2), 17 alpha-ethynylestradiol (EE2), 4-tert-octylphenol (4-t-OP) and 4-n-nonylphenol (4-n-NP) have been investigated in the laboratory using sediment and groundwater from an aquifer in Bolivar, South Australia. The sorption coefficients measured on the sediment were in the following order: 4-n-NP>4-t-OP>EE2>E2>BPA. The sorption coefficients (Kf values) for the five EDCs were 3.89, 21.8, 24.2, 90.9 and 195, respectively. The alkylphenols 4-t-OP and 4-n-NP had strong binding on the sediment while BPA had a weak affinity. Degradation experiments of the five EDCs showed that E2 and 4-n-NP degraded quickly under aerobic conditions with a half-life of 2 and 7 days, respectively. EE2 degraded slowly with an estimated half-life of 81 days in the aquifer material under aerobic conditions while the other two chemicals (BPA and 4-t-OP) remained almost unchanged. Little or no degradation of the five EDCs except slow degradation for E2 was observed within 70 days under anaerobic conditions in native groundwater.

Reduced plant uptake of pesticides with biochar additions to soil.

We investigated the effectiveness of two types of biochars in reducing the bioavailability of two soil-applied insecticides (chlorpyrifos and carbofuran) to Spring onion (Allium cepa). The biochars prepared from the pyrolysis of Eucalyptus spp. wood chips at 450 and 850 degrees C (BC850) were thoroughly mixed into the soil to achieve 0%, 0.1%, 0.5% and 1% by soil weight. A spring onion crop was grown for 5 wk in the biochar-amended soils spiked with 50 mgkg(-1) of each pesticide. The loss of both pesticides due to degradation and or sequestration in soils decreased significantly with increasing amounts of biochars in soil. Over 35 d, 86-88% of the pesticides were lost from the control soil, whereas it was only 51% of carbofuran and 44% of chlorpyrifos from the soil amended with 1.0% BC850. Despite greater persistence of the pesticide residues in biochar-amended soils, the plant uptake of pesticides decreased markedly with increasing biochar content of the soil. With 1% of BC850 soil amendment, the total plant residues for chlorpyrifos and carbofuran decreased to 10% and 25% of that in the control treatment, respectively. The BC850 was particularly effective in reducing phytoavailability of both pesticides from soil, due to its high affinity for and ability to sequester pesticide residues.

Sorption and degradation of estrogen‐like‐endocrine disrupting chemicals in soil

Studies were undertaken to assess sorption of seven endocrine-disrupting chemicals (EDCs), namely, estrone (E1), 17beta-estradiol (E2), estriol (E3), 17alpha-ethynylestradiol (EE2), bisphenol A (BPA), 4-tert-octyl phenol (4-t-OP), and 4-n-nonyl phenol (4-n-NP) on four soils (from sandy to clay soil) with different physicochemical properties and biodegradation of five EDCs (BPA, E2, EE2, 4-t-OP, and 4-n-NP) in a loam soil associated with wastewater reuse. We also characterized the biotransformation of E2 to El in the loam soil under aerobic and anaerobic conditions. Sorption test using a batch equilibrium method demonstrated that alkylphenols (4-t-OP and 4-n-NP) had the strongest sorption onto soils, followed by estrogens (EE2, E2, El, E3) and BPA. This laboratory study showed that all five EDCs, including the degradation product El, were degraded rapidly in the soil within 7 d under aerobic conditions. However, under anaerobic conditions in the soil, little or no degradation of the five EDCs was noted except for E2, which showed slow degradation during the 70-d study. The calculated half-lives for E2 under anaerobic conditions were 24 d in the soil. Estradiol was found to be biotransformed to E1 under both aerobic and anaerobic conditions. The study suggested that the five EDCs as well as El, which may be present in reclaimed wastewater, would not persist in well-aerated soil. But these EDCs persisting in anaerobic soil may affect soil and groundwater quality and ecosystem.

The role of biochar in modifying the environmental fate, bioavailability, and efficacy of pesticides in soils: a review

The role of biochar in sequestration of carbon, reducing the emission of greenhouse gases, and improving the soil fertility is increasingly being recognised and is leading to the recommendations of biochar amendment of soils. However, the implications of such amendments to the environmental fate and efficacy of pesticides are not well understood. The published work on the role of black carbon (which includes charcoal, soot, and other pyrolytic carbon materials) in the environmental fate and effect of organic contaminants is reviewed here, together with the studies on bioavailability and efficacy of some herbicides in soils amended with freshly produced biochars. Biochars, due to their unique properties especially their highly carbonaceous and aromatic nature and high specific surface area, have been reported to be up to >2000 times more effective than soil in sorbing pesticides. The incorporation of relatively small amounts of fresh biochars in soil (0.05% by wt) has also been shown to inhibit the microbial degradation of organic compounds including pesticides as well as reduce their plant availability and efficacy. Based on limited published research on biochars and related research on black carbon reviewed here, biochar amendments to soils are likely to reduce the bioavailability and efficacy of pesticides. Furthermore, these amendments can influence the potential accumulation and ecotoxicological impact of pesticides and other organic contaminants in the soil environment. The implications of heterogeneity and ageing of biochars applied to soils for sorption and desorption processes and in turn for other environmental fate processes need to be understood to seek the appropriate balance between carbon sequestration and pesticide efficacy. While biochar amendment of soil holds appeal from a carbon accounting and soil conditioning perspective, further research is urgently required to determine how biochar influences the efficacy and environmental fate of agrochemicals such as pesticides.

Characteristics of biochar and its application in remediation of contaminated soil

Biochar is produced by thermal decomposition of biomass under oxygen-limited conditions (pyrolysis), and it has received attention in soil remediation and waste disposal in recent years. The characteristics of biochar are influenced mainly by the preparation temperature and biomass. Higher pyrolysis temperature often results in the increased surface area and carbonized fraction of biochar leading to high sorption capability for pollutants. Biochars derived from various source materials show different properties of surface area, porosity and the amount of functional groups which are important concerning on the effect of biochar. Biochar has been proved to be effective in improving soil properties and increasing crop biomass. It has also been suggested that it can even enhance crop resistance to disease. Biochar has recently been used to remediate soil with both heavy metal and organic pollutants. The mechanism is electrostatic interaction and precipitation in the case of heavy metal, and the surface adsorption, partition and sequestration in the case of organic contaminants. However, application of biochar in soil has been shown to result in decreased efficacy of pesticides, which indicates a trade-off between the potentially promising effect of biochar on pesticide remediation and its negative effect on pesticide efficacy. While arguments on the effectiveness of biochar appear sound, further research is needed prior to widespread application of biochar in soil remediation.

Marked changes in herbicide sorption–desorption upon ageing of biochars in soil

We studied the sorption-desorption behaviour of two herbicides (diuron and artrazine) in a soil rich in Fe and Al oxides (Ferrosol), either amended freshly with two different types of biochars or that contained biochars aged under field conditions. Standard batch sorption-desorption experiments were conducted on soil samples freshly amended with two biochars, (namely, poultry litter - PL and paper mill - PM sludge) as well on those collected from field 32 months after biochar application. Soils that were freshly amended with biochars @ 10 t ha(-1) showed a two (PM) to five (PL) fold increase in sorption of herbicides as compared with that in the unamended soil. For example, the fresh amendments with PL biochar at 10 t ha(-1) led to a highly significant (P<0.001) increase in the Freundlich sorption coefficient (K(f)) of atrazine; i.e. 20.71 (n=0.40) as compared with 4.02 (n=0.70) for the control soil. Sorption was reversible in the unamended soil but sorption-desorption hysteresis was prominent in the soil amended with fresh biochars. In contrast, the soil containing aged biochars (at 10 t ha(-1)) exhibited sorption-desorption properties that were statistically similar to that of the control soil, especially for atrazine. Ageing of biochars in the soil over a 32 months period reduced the sorption capacity by 47% (PM) to 68% (PL) for diuron. These findings may have implications for herbicide efficacy in biochar amended soils.

Effect of Wastewater Treatment Plant Effluent on Microbial Function and Community Structure in the Sediment of a Freshwater Stream with Variable Seasonal Flow

ABSTRACT We investigated the effects of wastewater treatment plant (WWTP) discharge on the ecology of bacterial communities in the sediment of a small, low-gradient stream in South Australia. The quantification of genes involved in the biogeochemical cycling of carbon and nitrogen was used to assess potential impacts on ecosystem functions. The effects of disturbance on bacterial community structure were assessed by PCR-denaturing gradient gel electrophoresis of 16S rRNA genes, and clone library analysis was used to phylogenetically characterize significant shifts. Significant (P < 0.05) shifts in bacterial community structures were associated with alteration of the sediments physicochemical properties, particularly nutrient loading from the WWTP discharge. The effects were greatest at the sampling location 400 m downstream of the outfall where the stream flow is reduced. This highly affected stretch of sediment contained representatives of the gammaproteobacteria that were absent from less-disturbed sites, including Oceanospirillales and Methylococcaceae. 16S rRNA gene sequences from less-disturbed sites had representatives of the Caulobacteraceae, Sphingomonadaceae, and Nitrospirae which were not represented in samples from disturbed sediment. The diversity was lowest at the reference site; it increased with proximity to the WWTP outfall and declined toward highly disturbed (400 m downstream) sites (P < 0.05). The potential for biological transformations of N varied significantly with the stream sediment location (P < 0.05). The abundance of amoA, narG, and nifH genes increased with the distance downstream of the outfall. These processes are driven by N and C availability, as well as redox conditions. Together these data suggest cause and effect between nutrient loading into the creek, shift in bacterial communities through habitat change, and alteration of capacity for biogeochemical cycling of N.