Material and Methods Continuous Composter, Rotary Drum Composter (RD), Windrow and Feedstock Material configuration In order

to study the fate of pesticides during composting, a rotary drum composter (RD) of 250 L capacity (Kalamdhad and Kazmi, 2008) and a windrow composting system (W) L/W=6 (Yatish Kumar Singh et, al. 2009) was used (Fig. 1 & 2). The drum was made up of a 4 mm thick metal sheet having outer diameter and length of 0.9 and 0.92 m, respectively. The interior of the drum was coated with anti-corrosive paint. It was mounted on four rubber rollers attached to metal stand and manually rotated by handle. In order to provide better mixing conditions, 40 mm angles were welded longitudinally inside the drum. Two 10 cm holes were made to drain excess water. The mixed organic vegetable waste collected from vegetable market and shredded cow dung from nearby dairy plant and saw dust from a saw mill at Roorkee city (India). CN ratio of 22 was maintained in all cases. Following proper mixing on weight basis the material was made with the three different pesticides concentration by then adding Aldrin, Endosulfan,( and ) and Lindane in the waste i.e. Case 1(RD-1 and W-1): 1 mg/kg (concentration found in waste without addition), Case 2 (RD-2 and W-2): 6-7 mg/kg and Case 3 (RD-3 and W-3) 11 to 12 mg/kg. And finally 50% waste material loaded into the RD up to 70% of the total capacity and rest of 50% make a W with above mentioned configuration. In the rotary drum, one rotation was made per day.

Rotary Drum Composter (RD) : Schematic, Front view, Inside view.

Base width= 350mm

Top width= 100mm Height= 250mm

Length= 2100mm

Windrow Composting System

To observe the relationship between composting temperature and carbon dioxide emission, a large continuous composter was also used. An initial C/N of 24 was maintained and the drum was rotated once a day and also fed once a day.

Temperature Temperature was monitored on the basis of 24 hour time interval using a digital thermometer throughout the composting period within the continuous composter, and the thermometer was inserted into the composting mass in three different locations each time. Carbon Dioxide Carbon Dioxide concentration measurements were carried out on a daily interval basis throughout the composting process within the continuous composter. Pesticide Sample Preparation, Extraction and Analysis Samples were collected at 48 hour time intervals during all the cases from Rotary Drum composter (RD 2, RD 3), windrow and pile for the determination of selected four organochlorine pesticides Aldrin, Lindane, Endosulfan and Endosulfan and dried at room temperature for 24 hours. The dried sample ground with a mixture grinder and stored at -40C until use. Organochlorine pesticides (OCPs) were extracted from raw material and compost samples by ultrasonic agitation. The resulting extract was filtered through filter paper containing 5g of sodium sulfate to remove traces of water and was then concentrated to approximately 1 mL using a rotary evaporator. The volume of extract was adjusted to 2 mL with n-hexane and the final volume used for the pesticides analysis through GC-MS. Mass spectrometric analyses were carried out with a Varian GC-MS instrument (Germany). Kinetic Analysis The degradation kinetics of the three OCPs were analyzed using excel worksheet graphical tools. Endosulfanand are studied together as they are partially interchangeable isomers. The measured values of pesticide concentrations were compared with the best fit graphs of zero order, first order and second order degradation v/s time(days). The best fit graphs were found by using the average reaction rate constant calculated for each measured value. The analysis of the Temperature & CO2 correlation was also performed in excel worksheets. The observed relation was modeled using two different models, the Andrews and Kambhu/Haug model and the Ratkowsky et al. model. The analysis of the available data using monod kinetics was not possible, as the required microbial concentration parameters were not measured. The two models that were used are shown below:

Andrews and Kambhu/ Haug:

Rco2 = K[1(T-T1 ) - 2(T-T2)]

Rco2 = co2 evolution rate (g CO2/kg Vs-day) K = a parameter defined as the first order rate constant at reference temperature T1(day-1) T1, T2 = reference temperature parameters (C) 1, 2 = empirically estimated coefficients

Parameter K 1 2 T1 T2

Value taken 4.0656 1.03 1.09 20 60

Recommended 0.9*max obs rate 1.01-1.10 1.05-1.50 20C 40-70C

Ratkowsky et al.:

Rco2 = b(T-Tmin){1-e [c (T - Tmax)]}

Rco2 = CO2 evolution rate (g CO2/kg Vs-day) Tmax = maximum temperature for biodegradation Tmin = min temperature for biodegradation ( at Tmax and Tmin biodegradation rate is zero) b = an empirically estimated coefficient which determines the maximum rate for biodegradation c = an empirically estimated coefficient which determines the behaviour of the model near the optimum temperature
Parameter b c Value taken Recommended 0.3 0.0001-1.0 0.295 0.01-1.0 75 65 - 90C 34 0 - 25C

Tmax Tmin

The recommended values are recommendations of Richard & Walker*, except for T1, which is recommended by Oppenheimer*. The final values taken were found using a Box constrained search method. The objective was to minimize the sum of the squares of the error terms between the function and the fitted experimental data, as defined below:

(YTn - f(x)Tn )2 = sum of the error squared

The iterations were started using the final values taken by Richard & Walker* and 6 iterations were performed on each variable to arrive at the minimum sum of the squares of the error terms. This method directly allowed us to use these values to make the best fit curves for the Temperature CO2 correlation usig the above models. The final values of the error functions were then compared to evaluate the relative applicability of these models to the Continuous Composter. Results & Discussion Temperature is one of the key indicators of pesticides disappearance during composting. It determines the rate at which many of the biological processes take place. High temperature allows pesticides to easily get desorbed from organic matter and subsequently dissolve in aqueous phase of the composting material. This makes them accessible for degradation by microorganisms. The microbes are also increasingly active at higher temperatures, the peak of their activity falling between 60 and 75C. Microbial activity falls rapidly beyond the optimal temperature. This makes it important to study microbial activity w.r.t temperature, as finding an optimal temperature for microbial growth allows us to degrade pesticides faster at that temperature. Since the only source of CO2 in the composting process is exhalation by microbes, the CO2 evolution rate from the drum is taken as a direct measure of the number of microbes present and active in the compost material. Temperature & Carbon Dioxide In our study, the Andrews & Kambhu/Haug model was found to be the better fitting model as compared to the Ratkowsky model. The optimum temperature was found to be 62.1C by the Andrews & Kambhu/Haug model. This is also the more realistic model, as the value of T min comes
out to be around 0C instead the unrealistic value of 34C taken in the Ratkowsky model. The composter was found to be operating within the range of 58C and 70C which is within the desirable range from the optimum temperature. The results of the analysis are shown on the next page.

Days 7 11 15 22 24 26 28 32 34 36 38 41 43 45 47 50 52 54 58 60 62 64 68 72 76 80 84 88 91 93 99 104 107 112 117 123 129 136 141 145

Observations at Inlet of Drum CO2 Evolution Temperature 9.03 54 9.15 60.3 9.21 61.4 9.18 70.5 8.96 68.8 9.24 70.1 9.06 70.2 8.92 70.6 8.86 70.3 8.73 70 8.82 68.8 8.77 68.1 8.45 67.8 8.76 65.5 8.46 65.7 8.35 63.4 8.22 64.2 8.49 62.1 8.36 57.8 8.15 60.1 8.01 57.8 7.78 66 7.83 61.3 8.11 61.6 8.06 70.7 7.79 71 7.25 65.4 7.43 69.8 7.16 66.4 6.89 66.2 7.32 69.1 6.98 71.5 6.75 70.2 6.15 68.6 5.98 71.7 5.91 69.5 5.82 68 5.93 69.3 5.74 67.8 5.81 68.3

Calculated Rco2 values Haug Ratkowsky 8.68265 5.9877624 9.208188 7.7867812 9.235547 8.0712413 8.040043 8.0467249 8.522927 8.7636068 8.167913 8.2781462 8.136808 8.2244647 8.00662 7.9816101 8.105131 8.1680598 8.198455 8.3291897 8.522927 8.7636068 8.678739 8.8938069 8.738524 8.927738 9.072509 8.8767798 9.051487 8.8980815 9.214535 8.5320528 9.176464 8.6854878 9.239309 8.2424488 9.063695 7.0953226 9.200612 7.7334349 9.063695 7.0953226 9.017272 8.9251311 9.234109 8.0460927 9.237761 8.1210486 7.972602 7.9134024 7.866923 7.689206 9.082495 8.8652096 8.257865 8.4236907 8.96648 8.9511154 8.992628 8.9396416 8.448837 8.6826941 7.678332 7.2437 8.136808 8.2244647 8.569841 8.8087352 7.598386 7.0375506 8.342887 8.5476413 8.699121 8.9064534 8.396903 8.6192579 8.738524 8.927738 8.636593 8.8642863

In graphical form:
10

CO2 Evolution in mg/g/day

Haug experimental Ratkowsky

4 20 30 40 50 60 70 80

Temperature C
Pesticide Degradation During the OCPs degradation study, temperature increases from ambient to 60oC within 2 days during all the cases in rotary drum (RD 2, RD 3) as the rotary drum prevented escape of excessive heat generation. The temperature stayed above 50C until the 12th day. This causes higher microbial activity which degrades the pesticides at a greater rate as compare to windrow, in which temperature suddenly decreases from 55oC to 40oC within 4 to 6 days. As expected, this higher temperature which is closer to optimum indeed causes more efficient degradation. The removal efficiency at the end of 30 days is 82% and 89% for Aldrine in RD as compared to 76.4% in Windrow and 70.5% in Pile. The rotary drum composter also has other advantages which might have had an effect, as explained by Kalamdhad & Kazmi **. A similar pattern is followed in Lindane with RD efficiency hovering around 85%, Windrow efficiency at 77% and Pile efficiency at 71%. Endosulfan shows a slightly different trend, with the efficiency of all the methods dropping, but the efficiency of the RD composter is still better than windrow and pile. The efficiency of RD is 65.5% on average, for windrow, it is 59% and for pile, 60.5%. The decay curves for the two RD composters, windrow and pile are given below. The first order decay equation is found to be the best fit for them, thus their decay is taken to be of the first order reaction type. The graphical forms of the degradation curves for these pesticides along with their best fit curves are given from the next page.