Iron-impregnated granular activated carbon for arsenic removal: Application to practical column filters.

Arsenic is a major drinking water contaminant in many countries causing serious health hazards, and therefore, attempts are being made to remove it so that people have safe drinking water supplies. The effectiveness of arsenic removal from As(V) solutions using granular activated carbon (GAC) (zero point of charge (ZPC) pH 3.2) and iron incorporated GAC (GAC-Fe) (ZPC pH 8.0) was studied at 25 ±â€¯1 °C. The batch study confirmed that GAC-Fe had higher Langmuir adsorption capacity at pH 6 (1.43 mg As/g) than GAC (1.01 mg As/g). Adsorption data of GAC-Fe fitted the Freundlich model better than the Langmuir model, thus indicating the presence of heterogeneous adsorption sites. Weber and Morris plots of the kinetic adsorption data suggested intra-particle diffusion into meso and micro pores in GAC. The column adsorption study revealed that 2-4 times larger water volumes can be treated by GAC-Fe than GAC, reducing the arsenic concentration from 100 µg/L to the WHO guideline of 10 µg/L. The volume of water treated increased with a decrease in flow velocity and influent arsenic concentration. The study indicates the high potential of GAC-Fe to remove arsenic from contaminated drinking waters in practical column filters.

Polycyclic aromatic hydrocarbons in road-deposited sediments, water sediments, and soils in Sydney, Australia: Comparisons of concentration distribution, sources and potential toxicity.

Sixteen polycyclic aromatic hydrocarbons (PAHs) considered as priority environmental pollutants were analysed in surface natural soils (NS), road-deposited sediments (RDS), and water sediments (WS) at Kogarah in Sydney, Australia. Comparisons were made of their concentration distributions, likely sources and potential toxicities. The concentrations (mg/kg) in NS, RDS, and WS ranged from 0.40 to 7.49 (mean 2.80), 1.65 to 4.00 (mean 2.91), and 0.49 to 5.19 (mean 1.76), respectively. PAHs were dominated by relatively high molecular weight compounds with more than three fused benzene rings, indicating that high temperature combustion processes were their predominant sources. The proportions of high molecular weight PAHs with five or six fused benzene rings were higher in NS than in RDS, whereas the low molecular weight PAHs were higher in RDS. Concentrations of all PAHs compounds were observed to be the lowest in WS. The concentrations of most of the high molecular weight PAHs significantly correlated with each other in RDS and WS. All PAHs (except naphthalene) were significantly correlated in NS suggesting a common PAH source. Ratios for individual diagnostic PAHs demonstrated that the primary source of PAHs in WS and NS was of pyrogenic origin (combustion of petroleum (vehicle exhaust), grass, and wood) while in RDS it was petrogenic (i.e. unburned or leaked fuel and oil, road asphalt, and tyre particles) as well as pyrogenic. The potential toxicities of PAHs calculated using a toxicity equivalent quotient (TEQ) were all low but higher for NS compared to WS and RDS.

Use of wastewater alum-coagulation sludge as a phosphorus fertiliser - a mini review.

The use of aluminium (Al) salts, particularly alum, in coagulation is a widespread and conventional treatment method for eliminating pollutants, including phosphorus (P) which can cause eutrophication, from wastewater. However, a significant challenge of this process is the substantial amount of sludge generated, necessitating proper disposal. Historically, land disposal has been a common practice, but it poses potential issues for plant life on these lands. Despite the associated drawbacks, sludge contains elevated concentrations of vital plant nutrients like P and nitrogen, presenting an opportunity for beneficial use in agriculture. Given the imminent scarcity of P fertilizers due to the eventual depletion of high-grade P ores, this review explores the potential advantages and challenges of utilizing Al sludge as a P source for plants and proposes measures for its beneficial application. One primary concern with land application of Al sludge is its high levels of soluble Al, known to be toxic to plants, particularly in acidic soils. Another issue arises from the elevated Al concentration is P fixation and subsequently reducing P uptake by plants. To address these issues, soil treatment options such as lime, gypsum, and organic matter can be employed. Additionally, modifying the coagulation process by substituting part of the Al salts with cationic organic polymers proves effective in reducing the Al content of the sludge. The gradual release of P from sludge into the soil over time proves beneficial for plants with extended growth periods.

Enhanced removal of nitrate from water using surface modification of adsorbents--a review.

Elevated concentration of nitrate results in eutrophication of natural water bodies affecting the aquatic environment and reduces the quality of drinking water. This in turn causes harm to people's health, especially that of infants and livestock. Adsorbents with the high capacity to selectively adsorb nitrate are required to effectively remove nitrate from water. Surface modifications of adsorbents have been reported to enhance their adsorption of nitrate. The major techniques of surface modification are: protonation, impregnation of metals and metal oxides, grafting of amine groups, organic compounds including surfactant coating of aluminosilicate minerals, and heat treatment. This paper reviews current information on these techniques, compares the enhanced nitrate adsorption capacities achieved by the modifications, and the mechanisms of adsorption, and presents advantages and drawbacks of the techniques. Most studies on this subject have been conducted in batch experiments. These studies need to include continuous mode column trials which have more relevance to real operating systems and pilot-plant trials. Reusability of adsorbents is important for economic reasons and practical treatment applications. However, only limited information is available on the regeneration of surface modified adsorbents.

Submerged membrane/adsorption hybrid process in water reclamation and concentrate management-a mini review.

Clean water shortage is a major global problem due to escalating demand resulting from increasing human population growth and industrial activities, decreasing freshwater resources and persistent droughts. Recycling and reuse of wastewater by adopting efficient reclamation techniques can help solve this problem. However, wastewater contains a wide range of pollutants, which require removal before it may be reused. Adsorption and membrane processes are two successful treatments used to remove most of these pollutants. Their efficiency increases when these processes are integrated as observed, for example in a submerged membrane adsorption hybrid system (SMAHS). It uses coarse air bubbling/sparging to produce local shear which minimises reversible membrane fouling, improves performance and extends the life of the membrane. Additionally, the adsorbent acts as a buoyant media that produces an extra shearing effect on the membrane surface, reduces membrane resistance and increases flux. In addition, it adsorbs the organics that would otherwise deposit on and cause fouling of the membrane. The use of activated carbon (AC) adsorbent in SMAHS is very effective in removing most pollutants including natural organic matter (NOM) and organic micropollutants (OMPs) from wastewaters and membrane concentrate wastes, the latter being a serious problem in practical applications of the reverse osmosis process. However, certain NOM fractions and OMPs (i.e. hydrophilic and negatively charged ones) are not efficiently removed by AC. Other adsorbents need to be explored for their effective removal.

Treatment Trends and Combined Methods in Removing Pharmaceuticals and Personal Care Products from Wastewater-A Review.

When discharged into wastewater, pharmaceuticals and personal care products (PPCPs) become microorganic contaminants and are among the largest groups of emerging pollutants. Human, animal, and aquatic organisms' exposures to PPCPs have linked them to an array of carcinogenic, mutagenic, and reproductive toxicity risks. For this reason, various methods are being implemented to remove them from water bodies. This report critically reviews these methods and suggests improvements to removal strategies. Biological, physical, and chemical methods such as biological degradation, adsorption, membrane filtration, and advanced electrical and chemical oxidation are the common methods used. However, these processes were not integrated into most studies to take advantage of the different mechanisms specific to each process and are synergistic in the removal of the PPCPs that differ in their physical and chemical characteristics (charge, molecular weight, hydrophobicity, hydrogen bonding, structure). In the review articles published to date, very little information is available on the use of such integrated methods for removing PPCPs. This report attempts to fill this gap with our knowledge.

Bisphenols in water: Occurrence, effects, and mitigation strategies.

Bisphenols (bisphenol A (BPA), bisphenol S (BPS), bisphenol F (BPF) and bisphenol AF (BPAF)) are widely used as additives in numerous industries and therefore they are ubiquitously present throughout the world's natural environment including water. A review of the literature is presented on their sources, pathways of entry into the environment, and especially aquatic contexts, their toxicity to humans and other organisms and the technologies for removing them from water. The treatment technologies used are mostly adsorption, biodegradation, advanced oxidation, coagulation, and membrane separation processes. In the adsorption process, several adsorbents, especially carbon-based materials, have been tested. The biodegradation process has been deployed and it involves a variety of micro-organisms. Advanced oxidation processes (AOPs) such as UV/O3-based, catalysis relevant AOPs, electrochemical AOPs and physical AOPs have been employed. Both the biodegradation process and AOPs generate by-products which may be toxic. These by-products need to be subsequently removed using other treatment processes. Effectiveness of the membrane process varies depending on the porosity, charge, hydrophobicity, and other properties of the membrane. The problems and limitations of each treatment technique are discussed and methods to overcome them are presented. Suggestions are articulated to use a combination of processes to improve the removal efficiencies.

Ozonation/adsorption hybrid treatment system for improved removal of natural organic matter and organic micropollutants from water - A mini review and future perspectives.

Elevated concentrations of natural organic matter (NOM) and organic micropollutants (OMPs) can contaminate the quality of drinking water, and current water treatment technologies are not always successful in removing all their constituents. Ozonation and adsorption are two advanced processes with different removal mechanisms used to treat NOM and OMPs. Their treatment efficiency depends on the strength and kinetics of adsorption and ozonation (ozone molecule and OH radical (OH•) reaction) of the individual NOM constituents and OMPs. They are individually able to remove many of the NOM fractions and OMPs but not satisfactory in removing the vast array of their components which differ in their physico-chemical characteristics, for example molecular weight, charge, functional groups, aromaticity, and hydrophobicity/hydrophilicity. Significant progress has been made by integrating these processes (ozonation followed by activated carbon (AC) adsorption) but they need further improvement to efficiently target all NOM fractions and the various OMPs. Ozonation transforms the larger NOM molecules into smaller molecular sizes with lower aromaticity and hydrophobicity, subsequently resulting in reduced adsorption. The reduced adsorption of these molecules diminishes their competition against OMP adsorption resulting in increased OMP removal. Adsorption can remove unoxidized pollutants as well as the by-products of ozonation, and some of them are suspected to be human carcinogens. Of the commonly used adsorbents, anion exchange resin and AC, the former has higher affinity towards negatively charged humic fraction and OMPs. Conversely, the latter has higher affinity towards the hydrophobic constituents and smaller sized constituents which diffuse into AC pores and get adsorbed. Biofilm formed by long-term use of AC also contributes to enhanced removal of NOM and OMPs. This paper briefly reviews the currently available literature on removing NOM and OMPs by the ozonation/adsorption integrated process. It also suggests a new method for further increasing the efficiency of this process.

Removing ammonium from contaminated water using Purolite C100E: batch, column, and household filter studies.

Ammonium removal from drinking water to protect human and environmental health is one of the major global concerns. This study evaluates the performance of Purolite C100E, a commercial cation exchange resin, in eliminating ammonium in synthetic and real contaminated groundwater. The results demonstrate that the pH operation range of the resin for better ammonium removal is 3 to 8. Lower ammonium removal at low and high pH occurred due to competition from H+ and loss of ammonium as ammonia gas, respectively. Equilibrium data of ammonium removal fitted both the Langmuir and Freundlich isotherm models with the maximum Langmuir ion exchange capacities for initial ammonium concentrations of 10-200 mg/L and 50-2000 mg/L, reaching 18.37 mg/g and 40.16 mg/g, respectively. The presence of co-ions in the water reduced the ammonium removal efficiencies slightly (< 12%) in the order Mg2+ > Ca2+ > K+. The higher affinity of ammonium to adsorbent is due to its lower hydrated ionic radius and H-bonding. The maximum exchange capacity in the fluidized bed studies of the original Purolite C100E (bed height 27 cm, resin weight 75 g, initial ammonium concentration 17.4 mg/L, filtration velocity 0.5 m/h) was 10.48 mg/g. It progressively reduced slightly after three regeneration cycles to 8.79 mg/g. The column breakthrough data satisfactorily fitted the Thomas model. A household filter cartridge packed with 4 kg Purolite C100E (80 cm height) and operated at a filtration velocity of 1.9 m/h in Vietnam successfully reduced the initial 6 mg NH4+/L in groundwater (after sand filter pre-treatment) to well below the Vietnam drinking water standard (3 mg/L-QCVN 01:2009/BYT) continuously for 1 week, suggesting that such a filter can be adopted in rural areas to successfully remove ammonium from groundwater.

Seasonal influence on urban dust PAH profile and toxicity in Sydney, Australia.

Road dust is one of the major threats to the urban environment due to wash-off of dust to the surrounding catchments during wet weather period. The dust contains wide range of toxic contaminants such as heavy metals, polycyclic aromatic hydrocarbons (PAHS) and endocrine disrupting chemicals. Among the toxic contaminants, PAHs are of environmental concern due to their potential carcinogenic and mutagenic effect besides endocrine disruptive behaviour. Eighteen road dust samples from Sydney were collected in different time periods for a year and analysed for 16 US EPA PAHS. Total PAHs content range in the dust was 9-105 pg/g. Total and individual PAH contents were highest in the finest size fraction (<75 microm) and in winter compared to the other seasons. The PAH profiles in the different particle sizes were similar but different between the four seasons. The concentrations of higher molecular weight PAHS (4- and 5-rings) were much greater than the concentrations of lower molecular weight PAHs (2- and 3-rings). Toxicity equivalency factor application showed that the longer the dry weather period the higher the total PAHs content and toxicity in the dust.

Recovery of rare earth elements (Lu, Y) by adsorption using functionalized SBA-15 and MIL-101 (Cr).

Due to increasing application in the green energy sector, rare earth elements (REEs) have become a precious commodity in the international market. The REEs, Yttrium (Y) and Lutetium (Lu) are used as catalysts in wide array of industries. SBA-15 modified with 1,4-phthaloyl diamido-propyltriethoxysilane (1,4-PA-APTES) ligands; and chromium based metal organic frameworks (MOF) modified with PMIDA (MIL-101-PMIDA) were prepared in this study as potential adsorbents for recovery of these elements. The adsorption capacities for Lu and Y on virgin SBA-15 were negligible. After modification of SBA-15, the Langmuir adsorption capacities for Lu and Y significantly increased to 17.0 and 17.9 mg/L, respectively. The Langmuir adsorption capacities of Lu and Y on PMIDA modified MIL-101 (MIL-101-PMIDA) were 63.4 and 25.3 mg/g, respectively. Higher adsorption capacities of the MOF are due to its higher surface area (1050 m2/g) and beneficial functional groups such as phosphonic group present on the adsorbent surface and it attributes to rapider REE adsorption on MIL-101-PMIDA than on1,4-PA-SBA. Lu adsorption capacity was 2.5 times higher than Y due to its superior ion-exchange capability with grafted phosphonic groups. Both adsorbents retained over 90% of adsorption capacity after 5 adsorption/desorption cycles which demonstrate the high structural stability of the materials.

Removing arsenic from water with an original and modified natural manganese oxide ore: batch kinetic and equilibrium adsorption studies.

Arsenic contamination of drinking water is a serious water quality problem in many parts of the world. In this study, a low-cost manganese oxide ore from Vietnam (Vietnamese manganese oxide (VMO)) was firstly evaluated for its performance in arsenate (As(V)) removal from water. This material contains both Mn (25.6%) and Fe (16.1%) mainly in the form of cryptomelane and goethite minerals. At the initial As(V) concentration of 0.5 mg/L, the adsorption capacity of original VMO determined using the Langmuir model was 0.11 mg/g. The modified VMOs produced by coating VMO with iron oxide (Fea-VMO) and zirconium oxide (Zra-VMO) at 110 °C and 550 °C achieved the highest As(V) adsorption capacity when compared to three other methods of VMO modifications. Langmuir maximum adsorption capacities of Fea-VMO and Zra-VMO at pH 7.0 were 2.19 mg/g and 1.94 mg/g, respectively, nearly twenty times higher than that of the original VMO. Batch equilibrium adsorption data fitted well to the Langmuir, Freundlich, and Temkin models and batch kinetics adsorption data to pseudo-first order, pseudo-second order, and Elovich models. The increase of pH progressively from 3 to 10 reduced As(V) adsorption with a maximum reduction of 50-60% at pH 10 for both original and modified VMOs. The co-existing oxyanions considerably weakened the As(V) removal efficiency because they competed with As(V) anions. The competition order was PO43- > SiO32- > CO32- > SO42-. The characteristics of the original and modified VMOs evaluated using SEM, FTIR, XRD, XRF, surface area, and zeta potential explained the As(V) adsorption behaviour.

Iron and zirconium modified luffa fibre as an effective bioadsorbent to remove arsenic from drinking water.

Porous luffa plant fibre (LF) was grafted with Fe and Zr, and the ability of the fabricated adsorbents to remove arsenate (As(V)) from water was investigated in batch and column adsorption experiments. The Langmuir adsorption capacity (mg g-1) at pH 7 of LF was found to be 0.035, which increased to 2.55 and 2.89 after being grafted with Fe (FLF-3) and Zr (ZLF-3), respectively. Grafting with Fe and Zr increased the zeta potential and zero point of charge (ZPC) of LF (from pH 3.9 to 7.4 for Fe grafting and to 7.6 for Zr grafting), due to chemical bonding of the metals, possibly with the hydroxyl and carboxylic groups in LF as indicated in FTIR peaks. Zeta potential and ZPC decreased after As adsorption owing to inner-sphere complexation mechanism of adsorption. The increase of pH from 3 to 10 progressively reduced the adsorbents' adsorption capacity. Co-existing anions weakened the As(V) removal efficiency in the order, PO43- > SiO32- > CO32- > SO42-. Adsorption kinetics data fitted well to the Weber and Morris model, which revealed initial fast and subsequent slow rates of intra-particle As diffusion into the bigger pores and smaller pores, respectively. Column adsorption data fitted well to the Thomas model with the predicted adsorption capacities in the same order as in the batch adsorption experiment (ZLF-3 > FLF-3 > LF).

Removal of organic matter from wastewater reverse osmosis concentrate using granular activated carbon and anion exchange resin adsorbent columns in sequence.

Reverse osmosis concentrate (ROC) generated as a waste stream during reverse osmosis treatment of reclaimed wastewater, presents significant disposal challenges. This is because it causes environmental pollution when it is disposed to lands and natural water bodies. A long-term dynamic adsorption experiment was conducted by passing ROC from a wastewater reclamation plant, firstly through a granular activated carbon (GAC) column, and subsequently through an anion exchange resin (Purolite) column, for the removal of two major ROC pollutants, namely dissolved organic carbon (DOC) and microorganic pollutants (MOP). GAC removed most of the smaller-sized low molecular weight neutrals and building block fractions as well as the hydrophobic fraction of DOC with much less removal by the subsequent Purolite column. In contrast, the humics fraction was less well removed by the GAC column; however, Purolite column removed all that was remaining of this fraction. This study demonstrated that combining adsorbents having different affinities towards a variety of DOC fractions constitute an effective method of taking advantage of their different properties and achieving larger DOC removals. Almost 100% of all 17 MOPs were removed by the GAC column, even after 2880 bed volumes of continuous use. This contrasted with the DOC fractions' removal which was much lower.

Laterite as a low-cost adsorbent in a sustainable decentralized filtration system to remove arsenic from groundwater in Vietnam.

In the Red River Delta, Vietnam, arsenic (As) contamination of groundwater is a serious problem where more than seventeen million people are affected. Millions of people in this area are unable to access clean water from the existing centralized water treatment systems. They also cannot afford to buy expensive household water filters. Similar dangerous situations exist in many other countries and for this reason there is an urgent need to develop a cost-effective decentralized filtration system using new low-cost adsorbents for removing arsenic. In this study, seven locally available low-cost materials were tested for arsenic removal by conducting batch adsorption experiments. Of these materials, a natural laterite (48.7% Fe2O3 and 18.2% Al2O3) from Thach That (NLTT) was deemed the most suitable adsorbent based on arsenic removal performance, local availability, stability/low risk and cost (US$ 0.10/kg). Results demonstrated that the adsorption process was less dependent on the solution pH from 2.0 to 10. The coexisting anions competed with As(III) and As(V) in the order, phosphate > silicate > bicarbonate > sulphate > chloride. The adsorption process reached a fast equilibrium at approximately 120-360 min, depending on the initial arsenic concentrations. The Langmuir maximum adsorption capacities of NLTT at 30 °C were 512 µg/g for As(III) and 580 µg/g for As(V), respectively. Thermodynamic study conducted at 10 °C, 30 °C, and 50 °C suggested that the adsorption process of As(III) and As(V) was spontaneous and endothermic in nature. A water filtration system packed with NLTT was tested in a childcare centre in the most disadvantaged community in Ha Nam province, Vietnam, to determine arsenic removal performance in an operation lasting six months. Findings showed that the system reduced total arsenic concentration in groundwater from 122 to 237 µg/L to below the Vietnam drinking water standard of 10 µg/L.

Simultaneous removal of polycyclic aromatic hydrocarbons and heavy metals from water using granular activated carbon.

Polycyclic aromatic hydrocarbons (PAHs) and heavy metals are dangerous pollutants that commonly co-occur in water. An adsorption study conducted on the simultaneous removal of PAHs (acenaphthylene, phenanthrene) and heavy metals (Cd, Cu, Zn) by granular activated carbon (GAC) showed that, when these pollutants are present together, their adsorption was less than when they were present individually. The adsorptive removal percentage of PAHs (initial concentration 1 mg/L) was much higher than that of heavy metals (initial concentration (20 mg/L). The reduction in adsorption of PAHs by heavy metals followed the heavy metals' adsorption capacity and reduction in the negative zeta potential of GAC order (Cu > Zn > Cd). In contrast, PAHs had little effect on the zeta potential of GAC. The Langmuir adsorption capacities of acenaphthylene (0.31-2.63 mg/g) and phenanthrene (0.74-7.36 mg/g) on GAC decreased with increased metals' concentration with the reduction following the order of the metals' adsorption capacity. The kinetic adsorption data fitted to Weber and Morris plots, indicating intra-particle diffusion of both PAHs and heavy metals into the mesopores and micropores in GAC with the diffusion rates. This depended on the type of PAH and metal and whether the pollutants were present alone or together.

Simultaneous removal of natural organic matter and micro-organic pollutants from reverse osmosis concentrate using granular activated carbon.

Although reverse osmosis produces high quality reusable water from wastewater the rejected concentrate (ROC) poses potentially serious health hazards to non-target species. This is especially the case when it is disposed into aquatic environments due to the presence of high concentrations of dissolved natural organics, micro-organic pollutants (MOPs) and other pollutants. In batch and column studies we found that granular activated carbon (GAC) was very effective in simultaneously removing dissolved organic carbon (DOC) and 18 MOPs from ROC. The amounts of all DOC fractions adsorbed (0.01-3 mg/g) were much higher than those of the MOPs (0.01-2.5 µg/g) mainly because ROC contained larger concentrations of DOC fractions than MOPs. However, the partition coefficient which is a measure of the adsorbability was higher for most of the MOPs (0.21-21.6 L/g) than for the DOC fractions (0.01-0.45 L/g). The amount of DOC fraction adsorbed was in the order: humics > low molecular weights > building blocks > biopolymers (following mostly their concentrations in ROC). The partition coefficient was in the order: low molecular weigth nuetrals > humics > building blocks > biopolymers. The MOPs were classified into four groups based on their hydrophobicity (log Kow) and charge. The four positively charged MOPs with high hydrophobicity had the highest amounts adsorbed and partition coefficient, with 95-100% removal in the GAC column. The MOPs that are negatively charged, regardless of their hydrophobicity, had the lowest amounts adsorbed and partition coefficient with 73-94% removal.

Removing arsenic from water by coprecipitation with iron: Effect of arsenic and iron concentrations and adsorbent incorporation.

Arsenic (As) contamination of drinking water is a major cause of As toxicity in many parts of the world. A study was conducted to evaluate As removal from water containing 100-700 µg/L of As and As to Fe concentration ratios of 1:5-1:1000 using the coprecipitation process with and without As/Fe adsorption onto granular activated carbon (GAC). Fe concentration required to reduce As concentrations in order to achieve the WHO standard level of 10 µg/L increased exponentially with the increase in initial As concentration. When small amounts of GAC were added to the As/Fe solutions the Fe required to remove these As concentrations reduced drastically. This decline was due to the GAC adsorption of Fe and As, enhancing the removal of these metals through coprecipitation. Predictive regression equations were developed relating the GAC dose requirement to the initial As and Fe concentrations. Zeta potential data revealed that As was adsorbed on the GAC by outer-sphere complexation whereas Fe was adsorbed by inner-sphere complexation reversing the negative charge on GAC to positive values. X-ray diffraction of the GAC samples in the presence of Fe had an additional peak characteristic of ferrihydrite (Fe oxide) compared to that of the GAC sample without Fe. The study showed that incorporating an adsorbent into the coprecipitation process has the advantage of removing As from waters at all concentrations of Fe and As compared to coprecipitation alone which does not remove As to the required levels if Fe concentration is low.

Interrelationship among the pollutants in stormwater in an urban catchment and first flush identification using UV spectroscopy.

Assessing urban stormwater quality by investigation and characterisation of pollutants is a prerequisite for its effective management, for reuse and safe discharge. The stochastic nature of rainfall, dry weather periods, topology, human activities and climatic conditions generate and wash-off pollutants differently from event to event. This study investigated the major physico-chemical pollutants in stormwater runoff collected from an urban catchment over a period of two years. The aim of this study was to explore the use of UV spectroscopy to identify the first flush. In this study, the variation of pollutants during the passage of a rain event and the relationships among the measured pollutants was analysed to help broaden the application of UV spectroscopy beyond the detection of organic matter. Correlation analysis and principal component analysis (PCA) were performed to identify the possible relationship among measured pollutants. Although correlation analysis revealed some relationships between pollutants, in general they were not strong enough and was not helpful. PCA biplots suggested a few groups and revealed that the two components model could explain nearly 72% of the variability between pollutants. Pollutants in the group that included dissolved organic carbon (DOC) behaved in a similar manner. UV spectroscopy was applied to identify the first flush by comparing the recorded spectrum of consecutive samples that were collected in an event. Analysis of the spectra was able to isolate the point when first flush ends for DOC and pollutants that behave similar to it.

Pasture soils contaminated with fertilizer-derived cadmium and fluorine: livestock effects.

Fertilizers are indispensable for ensuring sustainability of agricultural production, thereby achieving food and fiber security. Nitrogen, sulfur, and potassium fertilizers are relatively free of impurities, but phosphorus (P) fertilizers, the main fertilizer input for the economic production of legume-based pastures, contain several contaminants, of which F and Cd are considered to be of most concern because they have potentially harmful effects on soil quality, livestock health, and food safety. Incidences of fluorosis in grazing livestock, and accumulation of Cd in the edible offal products of livestock, above the maximum permissible concentration set by food authorities have been reported in many countries. The majority of Cd and F applied to pastures in many countries continues to accumulate in the biologically active topsoil due to strong adsorption to soil constituents. However, the rate of Cd accumulation in the last decade has slowed as a result of selective use of low-Cd fertilizers. Cd and F adsorption in soils increase with increased contents of iron and aluminium oxides, layer silicates and allophane in soils, and increased soil pH. Cadmium adsorption also increases with increased Mn oxides and organic matter in soil. However, some Cd will be released during decomposition of plant and animal remains and organic matter. In most pastoral soils the majority of Cd and F added in fertilizers remains in the topsoil and little moves below 20-30 cm, and therefore these are unlikely to contaminate groundwater. However, F may pose a risk to shallow groundwater in very acidic low-P-fixing soils, and Cd may pose a risk in very acidic soils containing low organic matter and clay contents, or in soils with high chloride concentrations. Research is required both to test whether groundwater beneath farms with long histories of P fertilizer use is contaminated by these elements and also to examine their mechanisms of movement. Cd intake by grazing livestock occurs mostly by ingestion of pasture, and therefore measures to decrease plant availability of Cd in soils (e.g., maintaining high organic matter, reducing soil acidity and salinity, alleviating zinc deficiency, reducing weed) can reduce Cd accumulation in livestock. F intake by grazing livestock is mostly by soil ingestion; therefore, reducing soil ingestion by maintaining good pasture cover especially during winter periods can reduce F accumulation in livestock. In grazing livestock, Cd accumulates in kidney and liver, whereas F accumulates mainly in bones. Very little research has been carried out to study the effects of sustained but low levels of Cd and F additions on soil microbial activity, especially on the economically important N-fixers in symbiosis with pasture legumes and mycorrhizae. This subject also needs to be researched. The impact of F accumulation in bones of animals as influenced by the alternative low and high soil F intake between seasons and the effect of increasing age of animals needs further study to more accurately determine the potential risk of fluorosis and elucidate potential solutions to minimize F accumulation in bones and teeth of aged breeding stock. Computer-based models are required to identify farming systems that present a high risk of Cd concentrations in edible offal exceeding the MPC and livestock at risk of chronic fluorosis. A decision support model of this kind may be useful in developing management strategies capable of reducing Cd and F accumulation in animals. Preliminary empirical models have been developed for Cd (Loganathan et al. 1999) and F (Bretherton et al. 2002) accumulation in sheep grazing New Zealand pastures. Further development of these models is required for their wider applicability.