Residence time-dependent distribution patterns of hexachlorobenzene (HCB) and dichlorodiphenyltrichloroethane (DDT) among different soil organic matter fractions of three Chinese soils were investigated. Soil organic matter (SOM) was fractionated into fulvic acid (FA), humic acid (HA), bound-humic acid (BHA), lipid, and insoluble residue (IR) fractions using methyl isobutyl ketone (MIBK) method. Results revealed that as the residence time prolonged, the amounts of HCB and DDT in the FA, HA and BHA fractions decreased, while those in the lipid and IR fractions increased. One- and two-compartment first order, and one- and two-parameter pore-diffusion kinetic models were used to describe the mobility of HCB and DDT from the FA, HA and BHA fractions. The results suggest that excellent agreements were achieved between the experimental data and fits to the two-compartment first order kinetic model (R2 > 0.97). The transfer rates of HCB and DDT followed the order FA > HA > BHA. HCB and DDT tend to transfer from FA, HA and BHA fractions to lipid and IR fractions with increasing residence time.

Heavy metal pollution in sediments derived from the Deûle canal and sampled at different sites not far from a smelting plant has been examined in the present work in order to identify the sources of these metals and to assess the sediment environmental quality. The total concentrations of lead, zinc, cadmium, thallium, indium and tin in the samples were determined using inductively coupled plasma-atomic emission spectroscopy (ICP-AES). Our investigations have revealed that metal pollution is readily apparent in the studied sediments, with metals contents largely exceeding those measured in the background soils: maximum values are obtained for sediments collected near the industrial zone. The chemical forms of Pb, Zn, Cd, Tl, In and Sn in these sediments have also been studied using a sequential extraction method in order to evaluate their possible mobility, bioavailability and toxicity in this aquatic environment. Overall, the averaged fractionation of Pb and Zn is dominated, in a decreasing order, by the easily reducible, oxidizable and carbonate fractions. The importance of oxidizable phase (which is assumed to be composed mainly of organic matter and sulphides) in the Pb and Zn fractionations has been confirmed by the detection of X-ray diffraction peaks ascribed to galena (PbS) and wurtzite (ZnS) in contaminated sediment samples. Anthropogenic Tl, In, and Cd are mainly retained in Fe–Mn oxides/hydroxides, whereas anthropogenic Sn predominates in aluminosilicates/clays. We suspect that elevated percentage levels of Pb, Zn, Cd and In in the reducible fraction constitute a particular potential risk to this aquatic environment in case early diagenetic phenomena (that are observed in the sedimentary material) and physical disturbances (that occur in the water column) both take place strongly in the medium.

On 1998, a settling pond of a pyrite mine in Aznalcóllar (SW Spain) broke open, spilling some 3.6 × 10⁶ m³ of water and 0.9 × 10⁶ m³ of toxic tailings into the Agrio and Guadiamar river basin 40 km downstream, nearly to Doñana National Park. The soils throughout the basin were studied for arsenic pollution. Almost all the arsenic penetrated the soils in the solid phase (tailings) in variable amounts, mainly as a result of the different soil structure. The chemical oxidation of the tailings was the main cause of the pollution in these soils. A study of the relationships between the main soil characteristics and arsenic extracted with different reagents (water, CaCl₂, acetic acid, oxalic–oxalate and EDTA) indicates a direct relationship with the total arsenic concentration. The highest amount of arsenic was extracted by oxalic–oxalate (24%–36% of the total arsenic), indicating the binding with the iron oxides.

The potential for colloid-facilitated migration in contaminated sites is well known, and remediation techniques such as ultrafiltration are often considered for contaminant removal. Although this approach could be successful, the stability of the contaminant species in groundwater and the removal efficiency need to be investigated to ensure proper decontamination of moving aquifers. In our study, we have sampled contaminated groundwater near a former radioactive liquid disposal area at Chalk River, Ontario, Canada. Samples were taken in 2002 and 2004 to determine the behaviour of radiocontaminants by size fractionation using ultrafiltration, with emphasis on ⁶⁰Co and ¹³⁷Cs. The contaminant concentrations varied significantly for both contaminants in the two samples (34.5 and 25.5 Bq/l for ⁶⁰Co, 25.5 and 97.2 Bq/l for ¹³⁷Cs). On the other hand, the size fractionation (5,000 Daa nominal cut-off) remained consistent between the 2002 and 2004 samples, as most of the ⁶⁰Co (72%-83%) remained in the filtrate, while almost all of the ¹³⁷Cs (>98%) was retained along with the colloidal-sized material. Release of ⁶⁰Co and ¹³⁷Cs from the colloidal material yielded desorption coefficients (K D₋des) of 7.8 x 10⁵ and 1.7 x 10⁸ ml/g for ⁶⁰Co and ¹³⁷Cs, respectively.

GOAL, SCOPE AND BACKGROUND: Biosolids, i.e., treated sewage sludge, are commonly used as a fertilizer and amendment to improve soil productivity. Application of biosolids to meet the nitrogen (N) requirements of crops can lead to accumulation of phosphorus (P) in soils, which may result in P loss to water bodies. Since 1996, biosolids have been applied to a Pinus radiata D. Don plantation near Nelson City, New Zealand, in an N-deficient sandy soil. To investigate sustainability of the biosolids application programme, a long-term research trial was established in 1997, and biosolids were applied every three years, at three application rates, including control (no biosolids), standard and high treatments, based on total N loading. The objective of this study was to evaluate the effect of repeated application of biosolids on P mobility in the sandy soil. MATERIALS AND METHODS: Soil samples were collected in August 2004 from the trial site at depths of 0–10, 10–25, 25–50, 50–75, and 75–100 cm. The soil samples were analysed for total P (TP), plant-available P (Olsen P and Mehlich 3 P), and various P fractions (water-soluble, bioavailable, Fe and Al-bound, Ca-bound, and residual) using a sequential P fractionation procedure. RESULTS AND DISCUSSION: Soil TP and Olsen P in the high biosolids treatment (equivalent to 600 kg N ha⁻¹ applied every three years) had increased significantly (P<0.05) in both 0–10 cm and 10–25 cm layers. Mehlich 3 P in soil of the high treatment had increased significantly only at 0–10 cm. Olsen P appeared to be more sensitive than Mehlich 3 P as an indicator of P movement in a soil profile. Phosphorus fractionation revealed that inorganic P (Al/Fe-bound P and Ca-bound P) and residual P were the main P pools in soil, whereas water-soluble P accounted for approximately 70% of TP in biosolids. Little organic P was found in either the soil or biosolids. Concentrations of water-soluble P, bioavailable inorganic P (NaHCO₃ Pi) and potentially bioavailable inorganic P (NaOH Pi) in both 0–10 and 10–25 cm depths were significantly higher in the high biosolids treatment than in the control. Mass balance calculation indicated that most P applied with biosolids was retained by the top soil (0–25 cm). The standard biosolids treatment (equivalent to 300 kg N ha⁻¹ applied every three years) had no significant effect on concentrations of TP, Mehlich 3 P and Olsen P, and P fractions in soil. CONCLUSIONS: The results indicate that the soil had the capacity to retain most biosolids-derived P, and there was a minimal risk of P losses via leaching in the medium term in the sandy forest soil because of the repeated biosolids application, particularly at the standard rate. RECOMMENDATIONS AND PERSPECTIVES: Application to low-fertility forest land can be used as an environmentally friendly option for biosolids management. When biosolids are applied at a rate to meet the N requirement of the tree crop, it can take a very long time before the forest soil is saturated with P. However, when a biosolids product contains high concentrations of P and is applied at a high rate, the forest ecosystem may not have the capacity to retain all P applied with biosolids in the long term.

GOALS, SCOPE AND BACKGROUND: Anaerobic digestion of organic household waste can lead to an increase in dioxin-like content, as determined by dioxin-specific bioassays. This may be a result of bioactivation of Ah receptor (AhR) agonists into more potent congeners. Work towards identifying the contributing compound groups is important in order to understand the mechanisms and to assess the relevance behind this increase in dioxin-like toxicity, since the residue can be used as a soil fertilising agent. The aim with the present work was to identify compound groups with AhR agonistic properties that caused the previously reported increase in dioxin-like activity after anaerobic biodegradation METHODS: Firstly, chemical fractionation combined with dioxin bioassay testing was used to find bioactive classes of compounds. Secondly, batch digestion experiments with an externally added polychlorinated biphenyl (PCB) mixture (Clophen A50) and with decabrominated diphenyl ether (decaBDE), respectively, were studied as a possible process for transformation of precursors into more potent, dioxin-like compounds. Mesophilic (37ºC) and thermophilic (55ºC) anaerobic digestion were studied. Two different dioxin-specific bioassays were used to analyse AhR agonists in the biodegraded material, the CELCAD and the DR-CALUX. RESULTS AND DISCUSSION: AhR agonist activity was detected in both di- and polyaromatic fractions of digestate extracts, which indicated that a diverse mixture of compounds contributed to the bioassay responses. No quantifiable activities were induced by the monoaromatic fractions. Further fractionation based on planarity revealed higher concentrations of AhR agonists than what was detected after the first fractionation, probably due to non-additive biological interactions of compounds in the extract that were removed in the second fractionation. These results showed significant activity in the non-planar diaromatic fractions and in the co-planar fractions of both diaromates and polyaromates. In the batch experiment with externally added PCB, an increase in dioxin-like activity was seen after 21 days of digestion at mesophilic conditions. After completed digestion, the content of AhR agonists was equal to the start concentration. PCB analysis with GC-MS indicated that dehalogenation of PCBs occurred in the digestors. The batch experiment with decaBDE showed no significant changes in TEQ-concentrations over time. CONCLUSIONS: The results show that the previously reported increase of AhR agonists during mesophilic anaerobic digestion is probably due to an accumulation of several different groups of AhR agonists, both diaromatic and polyaromatic, and both co-planar and non-planar. Batch experiments with externally added PCBs and decaBDE, respectively, did not result in any accumulation of AhR agonist activity after completed digestion, even though chemical analysis indicate a dechlorination of PCBs. Complex, unfractionated extracts were difficult to test using the bioassay approach. Removal of AhR antagonists or otherwise interacting compounds during fractionation may yield bio-TEQ values that are much higher than in the original extract. RECOMMENDATIONS AND PERSPECTIVE: Our results indicate that the environmental risk that AhR agonists may pose concerning large-scale anaerobic digestion of organic household waste probably depends on the efficiency of the digester and the sludge residence time. In order to obtain reliable results with the bioassays, an extensive cleanup and fractionation procedure is necessary. Without clean up and fractionation, there is a risk for false negatives and misleading conclusions. DR-CALUX and CELCAD were both suitable for these kinds of studies, provided that suitable fractionation methods are used.